Ethylene/alpha-olefin block copolymers

ABSTRACT

Embodiments of the invention provide a class of ethylene/α-olefin block interpolymers. The ethylene/α-olefin interpolymers are characterized by an average block index, ABI, which is greater than zero and up to about 1.0 and a molecular weight distribution, M w /M n , greater than about 1.3. Preferably, the block index is from about 0.2 to about 1. In addition or alternatively, the block ethylene/α-olefin interpolymer is characterized by having at least one fraction obtained by Temperature Rising Elution Fractionation (‘TREF’), wherein the fraction has a block index greater than about 0.3 and up to about 1.0 and the ethylene/α-olefin interpolymer has a molecular weight distribution, M w /M n , greater than about 1.4.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority from U.S. Provisional Application Ser.No. 61/024,674 filed Jan. 30, 2008 (Attorney Docket No. 65044). Thisapplication is also related to the following U.S. Provisional PatentApplications also filed Jan. 30, 2008 with Ser. Nos. 61/024,688(Attorney Docket No. 66699), 61/024,693 (Attorney Docket No. 66700),61/024,698 (Attorney Docket No. 66701), 61/024,701 (Attorney Docket No.66702), and 61/024,705 (Attorney Docket No. 66703). For purposes ofUnited States patent practice, the contents of these applications areherein incorporated by reference in their entirety.

FIELD OF THE INVENTION

This invention relates to ethylene/α-olefin block interpolymers andarticles made from the block interpolymers.

BACKGROUND OF THE INVENTION

Block copolymers comprise sequences (“blocks”) of the same monomer unit,covalently bound to sequences of unlike type. The blocks can beconnected in a variety of ways, such as A-B in diblock and A-B-Atriblock structures, where A represents one block and B represents adifferent block. In a multi-block copolymer, A and B can be connected ina number of different ways and be repeated multiply. It may furthercomprise additional blocks of different type. Multi-block copolymers canbe either linear multi-block, multi-block star polymers (in which allblocks bond to the same atom or chemical moiety) or comb-like polymerswhere the B blocks are attached at one end to an A backbone.

A block copolymer is created when two or more polymer molecules ofdifferent chemical composition are covalently bonded to each other.While a wide variety of block copolymer architectures are possible, anumber of block copolymers involve the covalent bonding of hard plasticblocks, which are substantially crystalline or glassy, to elastomericblocks forming thermoplastic elastomers. Other block copolymers, such asrubber-rubber (elastomer-elastomer), glass-glass, and glass-crystallineblock copolymers, are also possible.

One method to make block copolymers is to produce a “living polymer”.Unlike typical Ziegler-Natta polymerization processes, livingpolymerization processes involve only initiation and propagation stepsand essentially lack chain terminating side reactions. This permits thesynthesis of predetermined and well-controlled structures desired in ablock copolymer. A polymer created in a “living” system can have anarrow or extremely narrow distribution of molecular weight and beessentially monodisperse (i.e., the molecular weight distribution isessentially one). Living catalyst systems are characterized by aninitiation rate which is on the order of or exceeds the propagationrate, and the absence of termination or transfer reactions. In addition,these catalyst systems are characterized by the presence of a singletype of active site. To produce a high yield of block copolymer in apolymerization process, such catalysts must exhibit livingcharacteristics to a substantial extent.

Butadiene-isoprene block copolymers have been synthesized via anionicpolymerization using the sequential monomer addition technique. Insequential addition, a certain amount of one of the monomers iscontacted with the catalyst. Once a first such monomer has reacted tosubstantial extinction forming the first block, a certain amount of thesecond monomer or monomer species is introduced and allowed to react toform the second block. The process may be repeated using the same orother anionically polymerizable monomers. However, ethylene and otherα-olefins, such as propylene, butene, 1-octene, etc., are not directlyblock polymerizable by anionic techniques.

Whenever crystallization occurs under quiescent conditions, which meansthat the polymer is not subjected to either external mechanical forcesor unusually fast cooling, homopolymers made from a highlycrystallizable monomer will crystallize from a melt and form sphericalstructures called “spherulites”. These spherulites range in size frommicrometers to millimeters in diameter. A description of this phenomenonmay be found in Woodward, A. E., Atlas of Polymer Morphology, HanserPublishers, New York, 1988. The spherulites are composed of layer likecrystallites called lamellae. Descriptions of this may be found inKeller, A., Sawada, S. Makromol. Chem., 74, 190 (1964) and Basset, D.C., Hodge, A. M., Olley, R. H., Proc. Roy. Soc. London, A377, p 25, 39,61 (1981). The spherulitic structure starts from a core of parallellamellae that subsequently branch and grow outward from the core in aradial direction. Disordered polymeric chains make up the materialbetween lamellar branches as described in Li, L., Chan, C., Yeung, K.L., Li, J., Ng, K., Lei, Y., Macromolecules, 34, 316 (2001).

Polyethylene and random α-olefin copolymers of ethylene can be forced toassume non-spherulitic morphologies in certain cases. One situationoccurs when the crystallization conditions are not quiescent, such asduring blown or cast film processing. In both cases, the melts aresubjected to strong external forces and fast cooling, which usuallyproduce row-nucleated or “shish-kebab” structures as described in A.Keller, M. J. Machin, J. Macromol. Sci. Phys., 1, 41 (1967). Anon-spherulitic morphology will also be obtained when the moleculescontain enough of an α-olefin or another type of comonomer to preventthe formation of lamellae. This change in crystal type occurs becausethe comonomers are usually too bulky to pack within an ethylene crystaland, therefore, a sequence of ethylene units in between comonomerscannot form a crystal any thicker than the length of that sequence in anall-trans conformation. Eventually, the lamellae would have to become sothin that chain folding into lamellar structures is no longer favorable.In this case, fringed micellar or bundled crystals are observed asdescribed in S. Bensason, J. Minick, A. Moet, S. Chum, A. Hiltner, E.Baer, J. Polym. Sci. B: Polym. Phys., 34, 1301 (1996). Studies of lowmolecular weight polyethylene fractions provide an understanding of thenumber of consecutive ethylene units that are required to form a chainfolded lamellae. As described in L. Mandelkern, A. Prasad, R. G. Alamo,G. M. Stack, Macromolecules, 23, 3696 (1990) polymer chain segments ofat least 100 ethylene units are required for chain folding. Below thisnumber of ethylene units, low molecular weight fractions form extendedchain crystals while polyethylene at typical molecular weights formsfringed micelles and creates a granular type morphology.

A fourth type of solid state polymer morphology has been observed inα-olefin block copolymers made by batch anionic polymerization ofbutadiene followed by hydrogenation of the resulting polymer. At thecrystallization temperature of the ethylene segments, the amorphousblocks can be either glassy or elastic. Studies of crystallizationwithin a glassy matrix have used styrene-ethylene (S-E) diblocks asdescribed in Cohen, R. E., Cheng, P. L., Douzinas, K., Kofinas, P.,Berney, C. V., Macromolecules, 23, 324 (1990) andethylene-vinylcyclohexane (E-VCH) diblocks as described in Loo, Y. L.,Register, R. A., Ryan, A. J., Dee G. T., Macromolecules 34, 8968 (2001).Crystallization within an elastic matrix has been studied usingethylene-(3-methyl-butene) diblocks as described in Quiram, D. J.,Register, R. A., Marchand, G. R., Ryan, A. J., Macromolecules 30, 8338(1997) and using ethylene-(styrene-ethylene-butene) diblocks asdescribed in Loo, Y. L., Register, R. A., Ryan, A. J., Macromolecules35, 2365 (2002). When the matrix was either glassy or was elastic butwith a high degree of segregation between the blocks, the solid statestructure showed the classical morphology of amorphous block copolymerssuch as styrene-butadiene-styrene (SBS), in which the different polymersegments were constrained into microdomains of approximately 25 nm indiameter. Crystallization of the ethylene segments in these systems wasprimarily constrained to the resulting microdomains. Microdomains cantake the form of spheres, cylinders, lamellae, or other morphologies.The narrowest dimension of a microdomain, such as perpendicular to theplane of lamellae, is constrained to <60 nm in these systems. It is moretypical to find constraints on the diameter of the spheres andcylinders, and the thickness of the lamellae to <30 nm Such materialsmay be referred to as microphase separated. FIG. 1 shows the predictedlamellar domain thickness for monodisperse ethylene/octene diblockcopolymers at different values of total molecular weight and Δ octenemole %. The figure demonstrates that, even at very large differences inoctene content of the blocks, molecular weights in excess of 180,000g/mol are necessary to achieve domain sizes of 50 nm. The high viscositywhich is unavoidable at such high molecular weights greatly complicatesthe production and processing of these materials. The calculationapplied the theoretical results of Matsen, M. W.; Bates, F. S.Macromolecules (1996) 29, 1091 at a temperature of 140° C., acharacteristic ratio of 7.5, and a melt density of 0.78 g/cm³. Thecorrelation between octene mole % and χ was determined using theexperimental results of Reichart, G. C. et al, Macromolecules (1998) 31,7886.

Block copolymers containing both crystalline and amorphous blocks cancrystallize from disordered, rather than microphase separated, melts andproduce a regular arrangement of crystalline lamellae as described inRangarajan, P., Register, R. A., Fetters, L. J. Macromolecules, 26, 4640(1993). The lamellar thickness of these materials is controlled by thecomposition and molecular weight of both blocks as described in theoriesby Dimarzio, E. A., Guttmann, C. M., Hoffman, J. D., Macromolecules, 13,1194 and Whitmore, M. D., Noolandi, J., Macromolecules, 21, 1482 (1988).For an ethylene based block copolymer, the maximum thickness of thecrystalline region of these morphologies is the same as the maximumthickness of a high density polyethylene crystal which is about 22 nm.

These materials based on batch anionic polymerization can beadditionally characterized as having very narrow molecular weightdistributions, typically with Mw/Mn <1.2, and correspondingly narrowmolecular weight distributions of their individual segments. They havealso only been examined in the form of diblock and triblock copolymerssince these are more readily synthesized via living anionicpolymerization than structures with higher numbers of blocks.

Block copolymers from olefin monomers prepared using livingpolymerization catalysts were recently reviewed by Domski, G. J.; Rose,J. M.; Coates, G. W.; Bolig, A. D.; Brookhart, M., in Prog. Polym. Sci.32, 30-92, (2007). Some of these monodisperse block copolymers alsoshowed the classical morphology of amorphous block copolymers such asstyrene-butadiene-styrene (SBS). Several of these block copolymerscontain crystallizable segments or blocks, and crystallization of thesegments in these systems was primarily constrained to the resultingmicrodomains. Syndiotacticpolypropylene-block-poly(ethylene-co-propylene) and syndiotacticpolypropylene-block-polyethylene, as described in Ruokolainen, J.,Mezzenga, R., Fredrickson, G. H., Kramer, E. J., Hustad, P. D., andCoates, G. W., in Macromolecules, 38(3); 851-86023 (2005), formmicrophase separated morphologies with domain sizes consistent withmonodisperse block copolymers (<60 nm). Similarly,polyethylene-block-poly(ethylene-co-propylene)s, as described byMatsugi, T.; Matsui, S.; Kojoh, S.; Takagi, Y.; Inoue, Y.; Nakano, T.;Fujita, T.; Kashiwa, N. in Macromolecules, 35(13); 4880-4887 (2002), aredescribed as having microphase separated morphologies. Atacticpolypropylene-block-poly(ethylene-co-propylene)s with narrow molecularweight distributions (Mw/Mn=1.07-1.3), as described in Fukui Y, MurataM. Appl. Catal. A 237, 1-10 (2002), are claimed to form microphaseseparated morphologies when blended with isotactic polypropylenes, withdomains of amorphous poly(ethylene-co-propylene) between 50-100 nm. Nomicrophase separation was observed in the bulk block copolymer.

Microphase separated diblock and triblock olefin block copolymers inwhich both block types are amorphous have also been prepared usingliving olefin polymerization techniques. A triblockpoly(1-hexene)-block-poly(methylene-1,3-cyclopentene)-block-poly(1-hexene)copolymer, as described by Jayaratne K. C., Keaton R. J., Henningsen D.A., Sita L. R., J. Am. Chem. Soc. 122, 10490-10491 (2000), withMn=30,900 g/mol and Mw/Mn=1.10 displayed a microphase separatedmorphology with cylinders of poly(methylene-1,3-cyclopentane) sizedabout 8 nm wide.Poly(methylene-1,3-cyclopentane-co-vinyltetramethylene)-block-poly(ethylene-co-norbornene)and poly(ethylene-co-propylene)-block-poly(ethylene-co-norbornene), asdescribed by Yoon, J.; Mathers, R. T.; Coates, G. W.; Thomas, E. L. inMacromolecules, 39(5), 1913-1919 (2006), also display microphaseseparated morphologies. Thepoly(methylene-1,3-cyclopentane-co-vinyltetramethylene)-block-poly(ethylene-co-norbornene),with Mn=450,000 g/mol and Mw/Mn=1.41, has alternating domains of 68 and102 nm, while thepoly(ethylene-co-propylene)-block-poly(ethylene-co-norbornene), withMn=576,000 g/mol and Mw/Mn=1.13, has domains sized 35-56 nm. Thesesamples demonstrate the difficulty in achieving domain sizes >60 nm, asvery high molecular weights are required to achieve such large domains.

Achieving microphase separated block copolymer morphologies usuallyrequires unfavorable dispersive interactions between the segments of thedifferent blocks, as characterized by the Flory-Huggins χ parameter, andhigh molecular weights. Representing the average block molecular weightas N, a typical narrow polydispersity diblock containing equal amountsby volume of the two blocks requires a value of χ times N greater than5.25 for the melt to display an ordered microphase morphology as shownby L. Leibler, Macromolecules 13, 1602 (1980). This minimum value of χNto achieve order increases to about 6 for triblock copolymers with equalvolumes of the two block types. As the number of blocks per moleculeincreases further, the required χN also increases and asymptoticallyapproaches 7.55 in the limit of a large number of blocks per molecule asshown by T. A. Kavassalis, M. D. Whitmore, Macromolecules 24, 5340(1991). Although multiblocks such as pentablocks have been shown toprovide a substantial improvement in mechanical properties as describedin T. J. Hermel, S. F. Hahn, K. A. Chaffin, W. W. Gerberich, F. S.Bates, Macromolecules 36, 2190 (2003), the overall molecular weight ofthese multiblocks has to be large in order to meet the requirements forordered melt morphologies. Since the energy requirements to process apolymer increase sharply with molecular weight, the commercialopportunities of such multiblocks may be limited.

However, theoretical studies by S. W. Sides, G. H. Fredrickson, J. Chem.Phys. 121, 4974 (2004) and D. M. Cooke, A. Shi, Macromolecules 39, 6661(2006) have shown that the minimum χN for ordered morphologies decreasesas the polydispersity of one or both of the block types is increased.When both block types have a most probable distribution of length, i.e.the ratio of weight average to number average block molecular weight is2, the minimum value of χN, where N is the number average block length,in order to achieve an ordered morphology is 2 for equal volumes of thetwo block types as shown by I. I. Potemkin, S. V. Panyukov, Phys. Rev.E. 57, 6902 (1998) for multiblocks in the mean-field limit. This lowervalue in χN translates to a substantial reduction in overall molecularweight for a melt ordered multiblock and, therefore, a drop inprocessing costs.

Another prediction of interest made by Potemkin, Panyukov and also byMatsen, M. W., Phys. Rev. Lett. 99, 148304 (2007) is that eachtransition in morphology, including the transition from disorder toorder, does not occur abruptly as in monodisperse block copolymers.Instead, there are regions of coexisting phases along each boundary.Along the order-order boundaries, the overall composition of a moleculemay determine how it partitions between phases. For example,polydisperse diblocks along the boundary between cylindrical andlamellar phases may have the more symmetric diblocks form lamellae whilethe asymmetric ones will tend to form cylinders. In the vicinity of theorder-disorder boundary, molecules with longer blocks may form anordered morphology while those with shorter blocks remain disordered. Insome cases, these disordered molecules may form a distinct macrophase.Alternatively, the location of these molecules could be directed to thecenter of the ordered domains in a similar manner to the domain swellingthat occurs when a homopolymer is blended with a block copolymer(Matsen, M. W., Macromolecules 28, 5765 (1995)).

In addition to achieving microphase separation at lower values of χN,block length polydispersity has also been hypothesized to have apronounced effect on the domain spacing of the ordered structures. Thesize of the microdomains in monodisperse block copolymers is largely afunction of the average molecular weight of a block, N, and is typicallyon the order of ˜20-50 nm. However, it has been predicted thatpolydispersity leads to larger domain spacings as compared withequivalent monodisperse block copolymers (Cooke, D. M.; Shi, A. C.Macromolecules, 39, 6661-6671 (2006); Matsen, M. W., Eur. Phys. J. E,21, 199-207 (2006)). The effects of polydispersity on phase behaviorhave also been demonstrated experimentally. Matsushita and coworkersapproximated polydispersity by blending a series of monodispersepolystyrene-b-poly(2-vinylpyridine)s (Noro, A.; Cho, D.; Takano, A.;Matsushita, Y. Macromolecules, 38, 4371-4376 (2005)). Register andcoworkers found ordered morphologies in a series ofpolystyrene-b-poly(acrylic acid)s synthesized using a controlled radicalpolymerization technique (Bendejacq, D.; Ponsinet, V.; Joanicot, M.;Loo, Y. L.; Register, R. A. Macromolecules, 35, 6645-6649 (2002)). Mostrecently, Lynd and Hillmyer (Lynd, N. A.; Hillmyer, M. A.Macromolecules, 38, 8803-8810 (2005)) evaluated a series of monodispersepoly(ethylene-alt-propylene)s that were chain extended with a block ofpoly(DL-lactide) using synthetic techniques that introducedpolydispersity in the poly(DL-lactide) block. In all of these examplespolydispersity led to increased domain spacings, suggesting that thelonger blocks have a greater role in determining domain size. In someinstances, polydispersity also produced changes in the type of orderedmorphology. The range of techniques for synthesis of polydisperse blockcopolymers is extremely limited, and it is especially difficult tointroduce polydispersity in multiple blocks while maintaining a highfraction of block copolymer.

The tendency for longer block lengths to have a greater role indetermining domain size, combined with the ability to swell domains,creates the potential for domain sizes that are much larger than what isobserved in typical monodisperse block copolymers. The ability for somemolecules to be ordered and others disordered contributes to theformation of swollen domains. The morphology of these systems can betermed block copolymer-directed mesophase separation.

It would be useful to provide an olefin block copolymer with an overallmolecular weight distribution and segment molecular weight distributionsuch that Mw/Mn >1.4, that is mesophase separated. It would also beuseful to provide such a material that is a multi-block copolymer with adistribution in the number of blocks.

In addition, there is an unfulfilled need for mesophase separated blockcopolymers which are based on ethylene and α-olefins. There is also aneed for block copolymers with low molecular weights (Mw<250,000 g/mol)that form domains larger than those from monodisperse block copolymersof the prior art, namely greater than 60 nm in the smallest dimension.There is also a need for a method of making such block copolymers.

SUMMARY OF THE INVENTION

The invention provides a composition comprising at least oneethylene/α-olefin block interpolymer, comprising one or more hard blocksand one or more soft blocks having a difference in mole percent α-olefincontent, wherein the ethylene/α-olefin block interpolymer ischaracterized by a molecular weight distribution, M_(w)/M_(n) in therange of from about 1.4 to about 2.8 and by an average block indexgreater than zero and up to about 1.0; and, wherein theethylene/α-olefin block interpolymer is mesophase separated.

The invention also provides an ethylene/α-olefin block interpolymercomprising one or more hard blocks and one or more soft blocks having adifference in mole percent α-olefin content wherein the copolymer ischaracterized by an average molecular weight of greater than 40,000g/mol, a molecular weight distribution, Mw/Mn, in the range of fromabout 1.4 to about 2.8, and a difference in mole percent α-olefincontent between the soft block and the hard block of greater than about18.5 mole percent.

The invention also provides an article made from the above describedethylene/α-olefin block copolymer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of the predicted thickness of each domain for amonodisperse ethylene/octene diblock copolymer made with 50% of eachblock type at different values of the backbone molecular weight, asmeasured by conventional GPC, and different levels of Δ octene mole %.

FIG. 2 is a plot constructed on the basis of the Flory equation forrandom ethylene/α-olefin copolymers to illustrate the definition of“block index.” “A” represents the whole, perfect random copolymer; “B”represents a pure “hard segment”; and “C” represents the whole, perfectblock copolymer having the same comonomer content as “A”. A, B, and Cdefine a triangular area within which most TREF fractions would fall.

FIG. 3 is a plot of natural log ethylene mole fraction for randomethylene/α-olefin copolymers as a function of the inverse of DSC peakmelting temperature or ATREF peak temperature. The filled squaresrepresent data points obtained from random homogeneously branchedethylene/α-olefin copolymers in ATREF; and the open squares representdata points obtained from random homogeneously branchedethylene/α-olefin copolymers in DSC. “P” is the ethylene mole fraction;“T” is the temperature in Kelvin.

FIG. 4 shows the melting point/density relationship for mesophaseseparated olefin block copolymers (represented by diamonds) as comparedto traditional random copolymers (represented by squares).

FIG. 5 shows plots of delta DSC-CRYSTAF as a function of DSC MeltEnthalpy for various polymers. The diamonds represent randomethylene/octene copolymers; and the circles represent polymer Examples29-40.

FIG. 6 shows the effect of density on elastic recovery for unorientedfilms made from olefin block copolymers (represented by the squares andcircles) and traditional copolymers (represented by the triangles whichare AFFINITY® polymers (The Dow Chemical Company)). The squaresrepresent inventive ethylene/butene copolymers; and the circlesrepresent inventive ethylene/octene copolymers.

FIG. 7 is a plot of octene content of Temperature Rising ElutionFractionation (“TREF”) fractionated ethylene/1-octene copolymerfractions versus TREF elution temperature of the fraction for thepolymer of Example 5 (represented by the circles) and comparativepolymers E and F (represented by the “X” symbols). The diamondsrepresent traditional random ethylene/octene copolymers.

FIG. 8 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus ATREF elution temperatureof the fraction for the polymer of Example 5 and for comparative F*. Thesquares represent Polymer Example F*; and the triangles representPolymer Example 5. Also shown is the ATREF temperature distribution forExample 5 (curve 1) and comparative F* (curve 2).

FIG. 9 is a graph of log storage modulus as a function of temperaturefor comparative ethylene/1-octene copolymer (curve 2) andpropylene/ethylene copolymer (curve 3) and for two ethylene/1-octeneblock copolymers made with differing quantities of chain shuttling agent(curves 1).

FIG. 10 is a plot of the block index calculated for each TREF fractionfor four polymers. The diamond represent Polymer F* with an averageblock index of 0; the triangles represent Polymer 5 with an averageblock index of 0.53; the squares represent Polymer 8 with an averageblock index of 0.59; and the “X” represents Polymer 20 with an averageblock index of 0.20.

FIG. 11 is a plot of the block index calculated for each TREF fractionfor two block copolymers: the filled bars represent Polymer 18B; and theopen bars represent Polymer 5.

FIG. 12 is a plot of the average block index calculated for ninedifferent polymers as a function of the diethyl zinc concentrationduring polymerization in terms of “[Zn/C₂H₄]*1000.” “x” represents anethylene/propylene block copolymer (Polymer 23); the two trianglesrepresent two ethylene/butene block copolymers (Polymer 21 and Polymer22); and the squares represent ethylene/octene copolymers made atdifferent levels of diethyl zinc (including one made without any diethylzinc).

FIG. 13 is a plot of the square root of the second moment about the meanweight average block index as a function of [Zn/C₂H₄]*1000.

FIG. 14 is a representation of a normal DSC profile for an olefin blockcopolymer.

FIG. 15 is a weighted DSC profile obtained by converting FIG. 14.

FIG. 16 is a ¹³C NMR spectrum of Polymer 19A.

FIG. 17 is a plot of I₁₀/I₂ as a function of the difference in octenecontent (mol %) of the hard and soft segments, referred to as Δ octenefor Examples 24-40.

FIG. 18 is an AFM image of Ex. 32 at ˜3,000× magnification.

FIG. 19 is an AFM image of Ex. 33 at a ˜3,000× magnification.

FIG. 20 shows an AFM image at ˜3,000× magnification of Ex. 34.

FIG. 21 is an AFM image of a styrenic block copolymer (SBC, 28 wt %styrene, 83 mol % “butane” in the B-block, M_(n)=64,000 g/mol) at30,000× magnification.

FIG. 22 shows a TEM image at ˜30,000× magnification of Ex. 34.

FIG. 23 shows reflectance spectra for Examples 35-38 and a comparativerandom copolymer AFFINITY® 1280G, available from The Dow ChemicalCompany. The random copolymer shows little reflectance (<10%) of thelight in the explored range, while the inventive examples show higherreflectance across this range.

FIG. 24 shows reflectance spectra for Examples 29, 30, 32, and 33 andthe comparative AFFINITY® 1280G, available from The Dow ChemicalCompany. The random copolymer shows little reflectance (<10%) of thelight in the explored range, while the inventive examples show higherreflectance across this range.

FIG. 25 shows reflectance spectra for Examples 34, 39, and 40 and thecomparative AFFINITY® 1280G, available from The Dow Chemical Company.The random copolymer shows little reflectance (<10%) of the light in theexplored range, while the inventive examples show higher reflectanceacross this range.

FIG. 26 shows reflectance spectra for Examples 25 and 26. These examplesshow little reflectance (<12%) of the light in the explored range.

FIG. 27 is a plot of Shore A vs Density for Examples 26, 27, 30 and 31.

FIG. 28 is a plot of Modulus vs Density for Examples 26, 27, 30 and 31.

FIG. 29 is a plot of 70° C. Compression Set vs Shore A for Examples 26,27, 30 and 31.

FIG. 30 is a plot of Tan δ as a function of temperature for Examples 26and 30.

FIG. 31 is a plot of Tan δ as a function of temperature for Examples 27and 31.

FIG. 32 is a plot of log storage modulus as a function of temperaturefor Examples 27 and 31.

FIG. 33 is a plot of 70° C. Compression Set vs Shore A for Blends 1, 2,3 and 4. Blends 1 and 2 comprise 35% OBC, 50% oil and 15% hPP and Blends3 and 4 comprise 28% OBC, 60% oil and 12% hPP.

FIG. 34 shows a plot of Heat of Fusion vs. ATREF Elution Temperature forfractions of random ethylene-octene copolymers and for fractions ofinventive Example 34.

FIG. 35 shows a plot of DSC Tm vs. mol % octene for ATREF fractions ofrandom ethylene-octene copolymers and for fractions of inventive Example34.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION General Definitions

“Polymer” means a polymeric compound prepared by polymerizing monomers,whether of the same or a different type. The generic term “polymer”embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as“interpolymer.”

“Interpolymer” means a polymer prepared by the polymerization of atleast two different types of monomers. The generic term “interpolymer”includes the term “copolymer” (which is usually employed to refer to apolymer prepared from two different monomers) as well as the term“terpolymer” (which is usually employed to refer to a polymer preparedfrom three different types of monomers). It also encompasses polymersmade by polymerizing four or more types of monomers.

The term “ethylene/α-olefin interpolymer” generally refers to polymerscomprising ethylene and an α-olefin having 3 or more carbon atoms.Preferably, ethylene comprises the majority mole fraction of the wholepolymer, i.e., ethylene comprises at least about 50 mole percent of thewhole polymer. More preferably, ethylene comprises at least about 60mole percent, at least about 70 mole percent, or at least about 80 molepercent, with the substantial remainder of the whole polymer comprisingat least one other comonomer that is preferably an α-olefin having 3 ormore carbon atoms. For many ethylene/octene copolymers, the preferredcomposition comprises an ethylene content greater than about 75 molepercent of the whole polymer and an octene content of from about 5 toabout 25, preferably from about 10 to about 20 mole percent of the wholepolymer, and more preferably from about 15 to about 20 mole percent ofthe whole polymer. For many ethylene/butene copolymers, the preferredcomposition comprises an ethylene content greater than about 60 molepercent of the whole polymer and a butene content of from about 10 toabout 40, preferably from about 20 to about 35 mole percent of the wholepolymer, and more preferably from about 25 to about 30 mole percent ofthe whole polymer. For many ethylene/propylene copolymers, the preferredcomposition comprises an ethylene content greater than about 40 molepercent of the whole polymer and a propylene content of from about 15 toabout 60, preferably from about 25 to about 50 mole percent of the wholepolymer, and more preferably from about 35 to about 45 mole percent ofthe whole polymer. In some embodiments, the ethylene/α-olefininterpolymers do not include those produced in low yields or in a minoramount or as a by-product of a chemical process. While theethylene/α-olefin interpolymers can be blended with one or morepolymers, the as-produced ethylene/α-olefin interpolymers aresubstantially pure and often comprise a major component of the reactionproduct of a polymerization process.

The term “crystalline” if employed, refers to a polymer or a segmentthat possesses a first order transition or crystalline melting point(Tm) as determined by differential scanning calorimetry (DSC) orequivalent technique. The term may be used interchangeably with the term“semicrystalline”. The crystals may exist as stacks of closely packedlamellar crystals, lamellae forming the arms of spherulites, or asisolated lamellar or fringed micellar crystals. The term “amorphous”refers to a polymer lacking a crystalline melting point as determined bydifferential scanning calorimetry (DSC) or equivalent technique.

The term “multi-block copolymer” or “segmented copolymer” refers to apolymer comprising two or more chemically distinct regions or segments(also referred to as “blocks”) preferably joined in a linear manner,that is, a polymer comprising chemically differentiated units which arejoined end-to-end with respect to polymerized ethylenic functionality,rather than in pendent or grafted fashion. In a preferred embodiment,the blocks differ in the amount or type of comonomer incorporatedtherein, the density, the amount of crystallinity, the crystallite sizeattributable to a polymer of such composition, the type or degree oftacticity (isotactic or syndiotactic), regio-regularity orregio-irregularity, the amount of branching, including long chainbranching or hyper-branching, the homogeneity, or any other chemical orphysical property. The multi-block copolymers are characterized byunique distributions of both polydispersity index (PDI or M_(w)/M_(n)),block length distribution, and/or block number distribution due to theunique process of making the copolymers. More specifically, whenproduced in a continuous process, the polymers desirably possess PDIfrom about 1.4 to about 8, preferably from about 1.4 to about 3.5, morepreferably from about 1.5 to about 2.5, and most preferably from about1.6 to about 2.5 or from about 1.6 to about 2.1. When produced in abatch or semi-batch process, the polymers possess PDI from about 1.4 toabout 2.9, preferably from about 1.4 to about 2.5, more preferably fromabout 1.4 to about 2.0, and most preferably from about 1.4 to about 1.8.It is noted that “block(s)” and “segment(s)” are used hereininterchangeably. In addition, the blocks of the polymer have a PDI inthe range of from about 1.4 to about 2.5, preferably in the range offrom about 1.4 to about 2.3, and more preferably in the range of fromabout 1.5 to about 2.3.

As used herein, “mesophase separation” means a process in whichpolymeric blocks are locally segregated to form ordered domains.Crystallization of the ethylene segments in these systems is primarilyconstrained to the resulting mesodomains and such systems may bereferred to as “mesophase separated”. These mesodomains can take theform of spheres, cylinders, lamellae, or other morphologies known forblock copolymers. The narrowest dimension of a domain, such asperpendicular to the plane of lamellae, is generally greater than about40 nm in the mesophase separated block copolymers of the instantinvention.

The ethylene/α-olefin block interpolymer may have a value of χN, where Nis the number average block length, in the range of from about 2 toabout 20, preferably in the range of from about 2.5 to about 15, andmore preferably in the range of from about 3 to about 10.

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or “approximate”is used in connection therewith. They may vary by 1 percent, 2 percent,5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical rangewith a lower limit, R^(L) and an upper limit, R^(U), is disclosed, anynumber falling within the range is specifically disclosed. Inparticular, the following numbers within the range are specificallydisclosed: R=R^(L)+k*(R^(U)−R^(L)), wherein k is a variable ranging from1 percent to 100 percent with a 1 percent increment, i.e., k is 1percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . , 50 percent,51 percent, 52 percent, . . . , 95 percent, 96 percent, 97 percent, 98percent, 99 percent, or 100 percent. Moreover, any numerical rangedefined by two R numbers as defined in the above is also specificallydisclosed.

Embodiments of the invention provide a new class of ethylene/α-olefinblock interpolymers (hereinafter “inventive polymer”, “ethylene/α-olefininterpolymers”, or variations thereof). The ethylene/α-olefininterpolymers comprise ethylene and one or more copolymerizable α-olefincomonomers in polymerized form, characterized by multiple blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties, wherein the polymers are mesophase separated.That is, the ethylene/α-olefin interpolymers are block interpolymers,preferably multi-block interpolymers or copolymers. The terms“interpolymer” and copolymer” are used interchangeably herein. In someembodiments, the multi-block copolymer can be represented by thefollowing formula:

(AB)_(n)

where n is at least 1, preferably an integer greater than 1, such as 2,3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, “A”represents a hard block or segment and “B” represents a soft block orsegment. Preferably, As and Bs are linked in a linear fashion, not in abranched or a star fashion. “Hard” segments refer to blocks ofpolymerized units in which ethylene is present in an amount greater than95 weight percent, and preferably greater than 98 weight percent. Inother words, the comonomer content in the hard segments is less than 5weight percent, and preferably less than 2 weight percent. In someembodiments, the hard segments comprise all or substantially allethylene. “Soft” segments, on the other hand, refer to blocks ofpolymerized units in which the comonomer content is greater than 5weight percent, preferably greater than 8 weight percent, greater than10 weight percent, or greater than 15 weight percent. In someembodiments, the comonomer content in the soft segments can be greaterthan 20 weight percent, greater than 25 weight percent, greater than 30weight percent, greater than 35 weight percent, greater than 40 weightpercent, greater than 45 weight percent, greater than 50 weight percent,or greater than 60 weight percent.

In some embodiments, A blocks and B blocks are randomly distributedalong the polymer chain. In other words, the block copolymers usually donot have a structure like:

AAA-AA-BBB-BB

In other embodiments, the block copolymers usually do not have a thirdtype of block. In still other embodiments, each of block A and block Bhas monomers or comonomers randomly distributed within the block. Inother words, neither block A nor block B comprises two or more segments(or sub-blocks) of distinct composition, such as a tip segment, whichhas a different composition than the rest of the block.

The ethylene/α-olefin interpolymers of the invention may becharacterized as mesophase separated. Domain sizes are typically in therange of from about 40 nm to about 300 nm, preferably in the range offrom about 50 nm to about 250 nm, and more preferably in the range offrom about 60 nm to about 200 nm, as measured by the smallest dimensionsuch as perpendicular to the plane of lamellae or the diameter ofspheres or cylinders. In addition, domains may have smallest dimensionsthat are greater than about 60 nm, greater than about 100 nm, andgreater than about 150 nm. Domains may be characterized as cylinders,spheres, lamellae, or other morphologies known for block copolymers. Themesophase separated polymers comprise olefin block copolymers whereinthe amount of comonomer in the soft segments as compared to that in thehard segments is such that the block copolymer undergoes mesophaseseparation in the melt. The required amount of comonomer may be measuredin mole percent and varies with each comonomer. A calculation may bemade for any desired comonomer in order to determine the amount requiredto achieve mesophase separation. The minimum level of incompatibility,expressed as χN, to achieve mesophase separation in these polydisperseblock copolymers is predicted to be χN=2.0 (LI. Potemkin, S. V.Panyukov, Phys. Rev. E. 57, 6902 (1998)). Recognizing that fluctuationsusually push the order-disorder transition in commercial blockcopolymers to slightly higher χN, a value χN=2.34 has been used as theminimum in the calculations below. Following the approach of D. J.Lohse, W. W. Graessley, Polymer Blends Volume 1: Formulation, ed. D. R.Paul, C. B. Bucknall, 2000, χN can be converted to the product of χ/νand M/ρ where ν is a reference volume, M is the number average blockmolecular weight and ρ is the melt density. The melt density is taken tobe 0.78 g/cm³ and a typical value of block molecular weight isapproximately 25,500 g/mol based on a diblock at an overall molecularweight of 51,000 g/mol. χ/ν for cases in which the comonomer is buteneor propylene is determined using 130° C. as the temperature and thenperforming an interpolation or extrapolation of the data provided inTable 8.1 in the reference by Lohse and Graessley. For each comonomertype, a linear regression in mole percent comonomer was performed. Forcases in which octene is the comonomer, the same procedure was performedwith the data of Reichart, G. C. et al, Macromolecules (1998), 31, 7886.The entanglement molecular weight at 413 K (about 140° C.) in kg/mol istaken to be 1.1. Using these parameters, the minimum difference incomonomer content is determined to be, respectively, 20.0, 30.8 or 40.7mole percent when the comonomer is octene, butene, or propylene. Whenthe comonomer is 1-octene, the difference in mole percent octene betweenthe hard segment and the soft segment, Δ octene, is greater than orequal to about 20.0 mole percent, more preferably greater than or equalto about 22 mole percent and may also be greater than or equal to about23 mole percent, greater than or equal to 24 mole percent, greater thanabout or equal to 25 mole percent and greater than about or equal to 26mole percent. In addition, the Δ octene value may be in the range offrom about 20.0 mole percent to about 60 mole percent and morepreferably in the range of from about 22 mole percent to about 45 molepercent. When the comonomer is 1-butene, the difference in mole percentbutene between the hard segment and the soft segment, Δ butene, isgreater than or equal to about 30.8 mole percent, more preferablygreater than or equal to about 33.9 mole percent and may also be greaterthan or equal to about 35.4 mole percent, greater than or equal to 36.9mole percent, greater than or equal to about 38.5 mole percent andgreater than or equal to about 40.0. In addition, the Δ butene value maybe in the range of from about 30.8 mole percent to about 80 molepercent, preferably in the range of from about 33.9 mole percent toabout 60 mole percent, preferably in the range of from about 36 molepercent to about 50 mole percent and more preferably in the range offrom about 37 mole percent to about 40 mole percent. When the comonomeris propylene, the difference in mole percent propylene between the hardsegment and the soft segment, Δ propylene, is greater than or equal toabout 40.7 mole percent, greater than or equal to about 44.7 molepercent, preferably greater than or equal to about 46.8 mole percent,more preferably greater than or equal to about 48.8 mole percent and mayalso be greater than or equal to about 50.9 mole percent, and greaterthan or equal to 52.9 mole percent. In addition, the Δ propylene valuemay be in the range of from about 40.7 mole percent to about 95 molepercent, preferably in the range of from about 44.7 mole percent toabout 65 mole percent and more preferably in the range of from about48.8 mole percent to about 60 mole percent.

The mesophase separated ethylene/α-olefin interpolymers may havecharacteristics of photonic crystals, periodic optical structuresdesigned to affect the motion of photons. Certain compositions of thesemesophase separated ethylene/α-olefin interpolymers appear pearlescentby eye. In some instances, films of the mesophase separatedethylene/α-olefin interpolymers reflect light across a band ofwavelengths in the range between about 200 nm to about 1200 nm. Forexample, certain films appear blue via reflected light but yellow viatransmitted light. Other compositions reflect light in the ultraviolet(UV) range, from about 200 nm to about 400 nm, while others reflectlight in the infrared (IR) range, from about 750 nm to about 1000 nm.

In some embodiments, the invention comprises a composition comprising atleast one ethylene/α-olefin block interpolymer, comprising one or morehard blocks and one or more soft blocks, wherein the ethylene/α-olefinblock interpolymer is characterized by a molecular weight distribution,M_(w)/M_(n), in the range of from about 1.4 to about 2.8 and:

(a) has at least one melting point, T_(m), in degrees Celsius, and adensity, d, in grams/cubic centimeter, wherein the numerical values ofT_(m) and d correspond to the relationship:

T _(m)>−6553.3+13735(d)−7051.7(d)², or

(b) is characterized by a heat of fusion, ΔH in J/g, and a deltaquantity, ΔT, in degrees Celsius, defined as the temperature differencebetween the tallest DSC peak and the tallest CRYSTAF peak, wherein thenumerical values of ΔT and ΔH have the following relationships:

ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,

ΔT≧48° C. for ΔH greater than 130 J/g,

wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or

(c) is characterized by an elastic recovery, Re, in percent at 300percent strain and 1 cycle measured with a compression-molded film ofthe ethylene/α-olefin interpolymer, and has a density, d, in grams/cubiccentimeter, wherein the numerical values of Re and d satisfy thefollowing relationship when ethylene/α-olefin interpolymer issubstantially free of a cross-linked phase:

Re>1481-1629(d); or

(d) has a molecular fraction which elutes between 40° C. and 130° C.when fractionated using TREF, characterized in that the fraction has amolar comonomer content of at least 5 percent higher than that of acomparable random ethylene interpolymer fraction eluting between thesame temperatures, wherein said comparable random ethylene interpolymerhas the same comonomer(s) and has a melt index, density, and molarcomonomer content (based on the whole polymer) within 10 percent of thatof the ethylene/α-olefin interpolymer; or

(e) has a storage modulus at 25° C., G′ (25° C.), and a storage modulusat 100° C., G′(100° C.), wherein the ratio of G′(25° C.) to G′ (100° C.)is in the range of about 1:1 to about 9:1; or

(f) is characterized by an average block index greater than zero and upto about 1.0; and,

wherein the ethylene/α-olefin block interpolymer is mesophase separated.

The ethylene/α-olefin interpolymers are characterized by an averageblock index, ABI, which is greater than zero and up to about 1.0 and amolecular weight distribution, M_(w)/M_(n), greater than about 1.3. Theaverage block index, ABI, is the weight average of the block index(“BI”) for each of the polymer fractions obtained in preparative TREF(i.e., fractionation of a polymer by Temperature Rising ElutionFractionation) from 20° C. and 110° C., with an increment of 5° C.(although other temperature increments, such as 1° C., 2° C., 10° C.,also can be used):

ABI=Σ(w _(i) BI _(i))

where BI_(i) is the block index for the i^(th) fraction of the inventiveethylene/α-olefin interpolymer obtained in preparative TREF, and w_(i)is the weight percentage of the i^(th) fraction. Similarly, the squareroot of the second moment about the mean, hereinafter referred to as thesecond moment weight average block index, can be defined as follows.

-   -   2^(nd) moment weight average

${BI} = \sqrt{\frac{\sum\limits_{\;}^{\;}\; \left( {w_{i}\left( {{BI}_{i} - {ABI}} \right)}^{2} \right)}{\frac{\left( {N - 1} \right){\sum\limits_{\;}^{\;}\; w_{i}}}{N}}}$

where N is defined as the number of fractions with BI_(i) greater thanzero. Referring to FIG. 2, for each polymer fraction, BI is defined byone of the two following equations (both of which give the same BIvalue):

${BI} = \frac{{1/T_{X}} - {1/T_{XO}}}{{1/T_{A}} - {1/T_{AB}}}$ or${BI} = {- \frac{{LnP}_{X} - {LnP}_{XO}}{{LnP}_{A} - {LnP}_{AB}}}$

where T_(X) is the ATREF (i.e., analytical TREF) elution temperature forthe i^(th) fraction (preferably expressed in Kelvin), P_(X) is theethylene mole fraction for the i^(th) fraction, which can be measured byNMR or IR as described below. P_(AB) is the ethylene mole fraction ofthe whole ethylene/α-olefin interpolymer (before fractionation), whichalso can be measured by NMR or IR. T_(A) and P_(A) are the ATREF elutiontemperature and the ethylene mole fraction for pure “hard segments”(which refer to the crystalline segments of the interpolymer). As anapproximation or for polymers where the “hard segment” composition isunknown, the T_(A) and P_(A) values are set to those for high densitypolyethylene homopolymer.

T_(AB) is the ATREF elution temperature for a random copolymer of thesame composition (having an ethylene mole fraction of P_(AB)) andmolecular weight as the inventive copolymer. T_(AB) can be calculatedfrom the mole fraction of ethylene (measured by NMR) using the followingequation:

LnP _(AB) =α/T _(AB)+β

where α and β are two constants which can be determined by a calibrationusing a number of well characterized preparative TREF fractions of abroad composition random copolymer and/or well characterized randomethylene copolymers with narrow composition. It should be noted that αand β may vary from instrument to instrument. Moreover, one would needto create an appropriate calibration curve with the polymer compositionof interest, using appropriate molecular weight ranges and comonomertype for the preparative TREF fractions and/or random copolymers used tocreate the calibration. There is a slight molecular weight effect. Ifthe calibration curve is obtained from similar molecular weight ranges,such effect would be essentially negligible. In some embodiments asillustrated in FIG. 3, random ethylene copolymers and/or preparativeTREF fractions of random copolymers satisfy the following relationship:

LnP=−237.83/T _(ATREF)+0.639

The above calibration equation relates the mole fraction of ethylene, P,to the analytical TREF elution temperature, T_(ATREF), for narrowcomposition random copolymers and/or preparative TREF fractions of broadcomposition random copolymers. T_(XO) is the ATREF temperature for arandom copolymer of the same composition (i.e., the same comonomer typeand content) and the same molecular weight and having an ethylene molefraction of P_(X). T_(XO) can be calculated from LnP_(X)=a/T_(XO)+β froma measured P_(X) mole fraction. Conversely, P_(XO) is the ethylene molefraction for a random copolymer of the same composition (i.e., the samecomonomer type and content) and the same molecular weight and having anATREF temperature of T_(X), which can be calculated from LnP_(XO)=a/T_(X)+13 using a measured value of T_(X).

Further description of the block index methodology is referenced inMacromolecular Symposia, Vol 257, (2007), pp 80-93 which is incorporatedby reference herein in its entirety.

Once the block index (BI) for each preparative TREF fraction isobtained, the weight average block index, ABI, for the whole polymer canbe calculated. In some embodiments, ABI is greater than zero but lessthan about 0.4 or from about 0.1 to about 0.3. In other embodiments, ABIis greater than about 0.4 and up to about 1.0. Preferably, ABI should bein the range of from about 0.4 to about 0.7, from about 0.5 to about0.7, or from about 0.6 to about 0.9. In some embodiments, ABI is in therange of from about 0.3 to about 0.9, from about 0.3 to about 0.8, orfrom about 0.3 to about 0.7, from about 0.3 to about 0.6, from about 0.3to about 0.5, or from about 0.3 to about 0.4. In other embodiments, ABIis in the range of from about 0.4 to about 1.0, from about 0.5 to about1.0, or from about 0.6 to about 1.0, from about 0.7 to about 1.0, fromabout 0.8 to about 1.0, or from about 0.9 to about 1.0.

Another characteristic of the inventive ethylene/α-olefin interpolymeris that the inventive ethylene/α-olefin interpolymer comprises at leastone polymer fraction which can be obtained by preparative TREF, whereinthe fraction has a block index greater than about 0.1 and up to about1.0 and the polymer having a molecular weight distribution, M_(w)/M_(n),greater than about 1.3. In some embodiments, the polymer fraction has ablock index greater than about 0.6 and up to about 1.0, greater thanabout 0.7 and up to about 1.0, greater than about 0.8 and up to about1.0, or greater than about 0.9 and up to about 1.0. In otherembodiments, the polymer fraction has a block index greater than about0.1 and up to about 1.0, greater than about 0.2 and up to about 1.0,greater than about 0.3 and up to about 1.0, greater than about 0.4 andup to about 1.0, or greater than about 0.4 and up to about 1.0. In stillother embodiments, the polymer fraction has a block index greater thanabout 0.1 and up to about 0.5, greater than about 0.2 and up to about0.5, greater than about 0.3 and up to about 0.5, or greater than about0.4 and up to about 0.5. In yet other embodiments, the polymer fractionhas a block index greater than about 0.2 and up to about 0.9, greaterthan about 0.3 and up to about 0.8, greater than about 0.4 and up toabout 0.7, or greater than about 0.5 and up to about 0.6.

In addition to an average block index and individual fraction blockindices, the ethylene/α-olefin interpolymers are characterized by one ormore of the properties described as follows.

In one aspect, the ethylene/α-olefin interpolymers used in embodimentsof the invention have a M_(w)/M_(n) from about 1.7 to about 3.5 and atleast one melting point, T_(m), in degrees Celsius and density, d, ingrams/cubic centimeter, wherein the numerical values of the variablescorrespond to the relationship:

T _(m)>−6553.3+13735(d)−7051.7(d)², and preferably

T _(m)≧−6880.9+14422(d)−7404.3(d)², and more preferably

T _(m)≧−7208.6−15109(d)-7756.9(d)².

Such melting point/density relationship is illustrated in FIG. 4. Unlikethe traditional random copolymers of ethylene/α-olefins whose meltingpoints decrease with decreasing densities, the inventive interpolymers(represented by diamonds) exhibit melting points substantiallyindependent of the density, particularly when density is between about0.87 g/cc to about 0.95 g/cc. For example, the melting point of suchpolymers are in the range of about 110° C. to about 125° C. when densityranges from 0.855 g/cc to about 0.895 g/cc. In some embodiments, themelting point of such polymers are in the range of about 110° C. toabout 125° C. when density ranges from 0.855 g/cc to about 0.895 g/cc.

In another aspect, the ethylene/α-olefin interpolymers comprise, inpolymerized form, ethylene and one or more α-olefins and arecharacterized by a ΔT, in degree Celsius, defined as the temperature forthe tallest Differential Scanning Calorimetry (“DSC”) peak minus thetemperature for the tallest Crystallization Analysis Fractionation(“CRYSTAF”) peak and a heat of fusion in J/g, ΔH, and ΔT and ΔH satisfythe following relationships:

ΔT>−0.1299(ΔH)+62.81, and preferably

ΔT≧−0.1299(ΔH)+64.38, and more preferably

ΔT≧−0.1299(ΔH)+65.95,

for ΔH up to 130 J/g. Moreover, ΔT is equal to or greater than 48° C.for ΔH greater than 130 J/g. The CRYSTAF peak is determined using atleast 5 percent of the cumulative polymer (that is, the peak mustrepresent at least 5 percent of the cumulative polymer), and if lessthan 5 percent of the polymer has an identifiable CRYSTAF peak, then theCRYSTAF temperature is 30° C., and ΔH is the numerical value of the heatof fusion in J/g. More preferably, the highest CRYSTAF peak contains atleast 10 percent of the cumulative polymer. FIG. 5 shows plotted datafor inventive polymers as well as comparative examples. Integrated peakareas and peak temperatures are calculated by the computerized drawingprogram supplied by the instrument maker. The diagonal line shown forthe random ethylene octene comparative polymers corresponds to theequation ΔT=−0.1299 (ΔH)+62.81.

In yet another aspect, the ethylene/α-olefin interpolymers have amolecular fraction which elutes between 40° C. and 130° C. whenfractionated using Temperature Rising Elution Fractionation (“TREF”),characterized in that said fraction has a molar comonomer contenthigher, preferably at least 5 percent higher, more preferably at least10 percent higher, than that of a comparable random ethyleneinterpolymer fraction eluting between the same temperatures, wherein thecomparable random ethylene interpolymer contains the same comonomer(s),and has a melt index, density, and molar comonomer content (based on thewhole polymer) within 10 percent of that of the block interpolymer.Preferably, the Mw/Mn of the comparable interpolymer is also within 10percent of that of the block interpolymer and/or the comparableinterpolymer has a total comonomer content within 10 weight percent ofthat of the block interpolymer.

In still another aspect, the ethylene/α-olefin interpolymers arecharacterized by an elastic recovery, Re, in percent at 300 percentstrain and 1 cycle measured on a compression-molded film of anethylene/α-olefin interpolymer, and has a density, d, in grams/cubiccentimeter, wherein the numerical values of Re and d satisfy thefollowing relationship when ethylene/α-olefin interpolymer issubstantially free of a cross-linked phase:

Re≧1481-1629(d); and preferably

Re≧1491-1629(d); and more preferably

Re≧1501-1629(d); and even more preferably

Re≧1511-1629(d).

FIG. 6 shows the effect of density on elastic recovery for unorientedfilms made from certain block interpolymers and traditional randomcopolymers. For the same density, the block interpolymers havesubstantially higher elastic recoveries.

In some embodiments, the ethylene/α-olefin interpolymers have anelongation at break of at least 600 percent, more preferably at least700 percent, highly preferably at least 800 percent, and most highlypreferably at least 900 percent at a crosshead separation rate of 11cm/minute.

In other embodiments, the ethylene/α-olefin interpolymers have (1) astorage modulus ratio, G′(25° C.)/G′(100° C.), of from 1 to 20,preferably from 1 to 10, more preferably from 1 to 5; and/or (2) a 70°C. compression set of less than 80 percent, preferably less than 70percent, especially less than 60 percent, less than 50 percent, or lessthan 40 percent, down to a compression set of 0 percent.

In still other embodiments, the ethylene/α-olefin interpolymers have a70° C. compression set of less than 80 percent, less than 70 percent,less than 60 percent, or less than 50 percent. Preferably, the 70° C.compression set of the interpolymers is less than 40 percent, less than30 percent, less than 20 percent, and may go down to about 0 percent.

In other embodiments, the ethylene/α-olefin interpolymers comprise, inpolymerized form, at least 50 mole percent ethylene and have a 70° C.compression set of less than 80 percent, preferably less than 70 percentor less than 60 percent, most preferably less than 40 to 50 percent anddown to close to zero percent.

In some embodiments, the multi-block copolymers possess a PDI fitting aSchultz-Flory distribution rather than a Poisson distribution. Thecopolymers are further characterized as having both a polydisperse blockdistribution and a polydisperse distribution of block sizes andpossessing a most probable distribution of block lengths. Preferredmulti-block copolymers are those containing 4 or more blocks or segmentsincluding terminal blocks. More preferably, the copolymers include atleast 5, 10 or 20 blocks or segments including terminal blocks.

In addition, the inventive block interpolymers have additionalcharacteristics or properties. In one aspect, the interpolymers,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, are characterized by multiple blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties (blocked interpolymer), most preferably amulti-block copolymer, said block interpolymer having a molecularfraction which elutes between 40° C. and 130° C. when fractionated usingTREF, characterized in that said fraction has a molar comonomer contenthigher, preferably at least 5 percent higher, more preferably at least10 percent higher, than that of a comparable random ethyleneinterpolymer fraction eluting between the same temperatures, whereinsaid comparable random ethylene interpolymer comprises the samecomonomer(s), and has a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (“NMR”) spectroscopypreferred. Moreover, for polymers or blends of polymers havingrelatively broad TREF curves, the polymer is first fractionated usingTREF into fractions each having an eluted temperature range of 10° C. orless. That is, each eluted fraction has a collection temperature windowof 10° C. or less. Using this technique, said block interpolymers haveat least one such fraction having a higher molar comonomer content thana corresponding fraction of the comparable interpolymer.

In another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks (i.e.,at least two blocks) or segments of two or more polymerized monomerunits differing in chemical or physical properties (blockedinterpolymer), most preferably a multi-block copolymer, said blockinterpolymer having a peak (but not just a molecular fraction) whichelutes between 40° C. and 130° C. (but without collecting and/orisolating individual fractions), characterized in that said peak, has acomonomer content estimated by infra-red spectroscopy when expandedusing a full width/half maximum (FWHM) area calculation, has an averagemolar comonomer content higher, preferably at least 5 percent higher,more preferably at least 10 percent higher, than that of a comparablerandom ethylene interpolymer peak at the same elution temperature andexpanded using a full width/half maximum (FWHM) area calculation,wherein said comparable random ethylene interpolymer has the samecomonomer(s) and has a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer. The full width/half maximum(FWHM) calculation is based on the ratio of methyl to methylene responsearea [CH₃/CH₂] from the ATREF infra-red detector, wherein the tallest(highest) peak is identified from the base line, and then the FWHM areais determined. For a distribution measured using an ATREF peak, the FWHMarea is defined as the area under the curve between T₁ and T₂, where T₁and T₂ are points determined, to the left and right of the ATREF peak,by dividing the peak height by two, and then drawing a line horizontalto the base line, that intersects the left and right portions of theATREF curve. A calibration curve for comonomer content is made usingrandom ethylene/α-olefin copolymers, plotting comonomer content from NMRversus FWHM area ratio of the TREF peak. For this infra-red method, thecalibration curve is generated for the same comonomer type of interest.The comonomer content of TREF peak of the inventive polymer can bedetermined by referencing this calibration curve using its FWHM methyl:methylene area ratio [CH₃/CH₂] of the TREF peak.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (NMR) spectroscopypreferred. Using this technique, said blocked interpolymer has a highermolar comonomer content than a corresponding comparable interpolymer.

Preferably, for interpolymers of ethylene and 1-octene, the blockinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity (−0.2013)T+20.07, more preferably greater than or equal to the quantity (−0.2013)T+21.07, where T is the numerical value of the peak elution temperatureof the TREF fraction being compared, measured in ° C.

FIG. 7 graphically depicts an embodiment of the block interpolymers ofethylene and 1-octene where a plot of the comonomer content versus TREFelution temperature for several comparable ethylene/1-octeneinterpolymers (random copolymers) are fit to a line representing(−0.2013) T+20.07 (solid line). The line for the equation (−0.2013)T+21.07 is depicted by a dotted line. Also depicted are the comonomercontents for fractions of a block ethylene/1-octene interpolymer. All ofthe block interpolymer fractions have significantly higher 1-octenecontent than either line at equivalent elution temperatures. This resultis characteristic of the olefin block copolymer and is believed to bedue to the presence of differentiated blocks within the polymer chains,having both crystalline and amorphous nature.

FIG. 8 graphically displays the TREF curve and comonomer contents ofpolymer fractions for Example 5 and comparative F to be discussed below.The peak eluting from 40° C. to 130° C., preferably from 60° C. to 95°C. for both polymers is fractionated in 5° C. increments. Actual datafor three of the fractions for Example 5 are represented by triangles.The skilled artisan can appreciate that an appropriate calibration curvemay be constructed for interpolymers with differing comonomer contentfitted to the ATREF temperature values. Preferably, such calibrationcurve is obtained using comparative interpolymers of the same monomers,preferably random copolymers made using a metallocene or otherhomogeneous catalyst composition. The olefin block copolymers arecharacterized by a molar comonomer content greater than the valuedetermined from the calibration curve at the same ATREF elutiontemperature, preferably at least 5 percent greater, more preferably atleast 10 percent greater.

In addition to the above aspects and properties described herein, theinventive polymers can be characterized by one or more additionalcharacteristics. In one aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that said fractionhas a molar comonomer content higher, preferably at least 5 percenthigher, more preferably at least 10, 15, 20 or 25 percent higher, thanthat of a comparable random ethylene interpolymer fraction elutingbetween the same temperatures, wherein said comparable random ethyleneinterpolymer comprises the same comonomer(s), preferably it is the samecomonomer(s), and a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer.

Preferably, the above interpolymers are interpolymers of ethylene and atleast one α-olefin, especially those interpolymers having a wholepolymer density from about 0.855 to about 0.935 g/cm³, and moreespecially for polymers having more than about 1 mole percent comonomer,the blocked interpolymer has a comonomer content of the TREF fractioneluting between 40 and 130° C. greater than or equal to the quantity(−0.1356) T+13.89, more preferably greater than or equal to the quantity(−0.1356) T+14.93, and most preferably greater than or equal to thequantity (−0.2013)T+21.07, where T is the numerical value of the peakATREF elution temperature of the TREF fraction being compared, measuredin ° C.

In still another aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that every fractionhaving a comonomer content of at least about 6 mole percent, has amelting point greater than about 100° C. For those fractions having acomonomer content from about 3 mole percent to about 6 mole percent,every fraction has a DSC melting point of about 110° C. or higher. Morepreferably, said polymer fractions, having at least 1 mol percentcomonomer, has a DSC melting point that corresponds to the equation:

Tm≧(−5.5926)(mol percent comonomer in the fraction)+135.90.

In yet another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties (blocked interpolymer), most preferably amulti-block copolymer, said block interpolymer having a molecularfraction which elutes between 40° C. and 130° C., when fractionatedusing TREF increments, characterized in that every fraction that has anATREF elution temperature greater than or equal to about 76° C., has amelt enthalpy (heat of fusion) as measured by DSC, corresponding to theequation:

Heat of fusion(J/gm)≦(3.1718)(ATREF elution temperature inCelsius)−136.58,

The inventive block interpolymers have a molecular fraction which elutesbetween 40° C. and 130° C., when fractionated using TREF increments,characterized in that every fraction that has an ATREF elutiontemperature between 40° C. and less than about 76° C., has a meltenthalpy (heat of fusion) as measured by DSC, corresponding to theequation:

Heat of fusion(J/gm)≦(1.1312)(ATREF elution temperature inCelsius)+22.97.

ATREF Peak Comonomer Composition Measurement by Infra-Red Detector

The comonomer composition of the TREF peak can be measured using an IR4infra-red detector available from Polymer Char, Valencia, Spain(http://www.polymerchar.com/).

The “composition mode” of the detector is equipped with a measurementsensor (CH₂) and composition sensor (CH₃) that are fixed narrow bandinfra-red filters in the region of 2800-3000 cm⁻¹. The measurementsensor detects the methylene (CH₂) carbons on the polymer (whichdirectly relates to the polymer concentration in solution) while thecomposition sensor detects the methyl (CH₃) groups of the polymer. Themathematical ratio of the composition signal (CH₃) divided by themeasurement signal (CH₂) is sensitive to the comonomer content of themeasured polymer in solution and its response is calibrated with knownethylene alpha-olefin copolymer standards.

The detector when used with an ATREF instrument provides both aconcentration (CH₂) and composition (CH₃) signal response of the elutedpolymer during the TREF process. A polymer specific calibration can becreated by measuring the area ratio of the CH₃ to CH₂ for polymers withknown comonomer content (preferably measured by NMR). The comonomercontent of an ATREF peak of a polymer can be estimated by applying thereference calibration of the ratio of the areas for the individual CH₃and CH₂ response (i.e. area ratio CH₃/CH₂ versus comonomer content).

The area of the peaks can be calculated using a full width/half maximum(FWHM) calculation after applying the appropriate baselines to integratethe individual signal responses from the TREF chromatogram. The fullwidth/half maximum calculation is based on the ratio of methyl tomethylene response area [CH₃/CH₂] from the ATREF infra-red detector,wherein the tallest (highest) peak is identified from the base line, andthen the FWHM area is determined. For a distribution measured using anATREF peak, the FWHM area is defined as the area under the curve betweenT1 and T2, where T1 and T2 are points determined, to the left and rightof the ATREF peak, by dividing the peak height by two, and then drawinga line horizontal to the base line, that intersects the left and rightportions of the ATREF curve.

The application of infra-red spectroscopy to measure the comonomercontent of polymers in this ATREF-infra-red method is, in principle,similar to that of GPC/FTIR systems as described in the followingreferences: Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley;“Development of gel-permeation chromatography-Fourier transform infraredspectroscopy for characterization of ethylene-based polyolefincopolymers”, Polymeric Materials Science and Engineering (1991), 65,98-100.; and Deslauriers, P. J.; Rohlfing, D. C.; Shieh, E. T.;“Quantifying short chain branching microstructures in ethylene-1-olefincopolymers using size exclusion chromatography and Fourier transforminfrared spectroscopy (SEC-FTIR)”, Polymer (2002), 43, 59-170, both ofwhich are incorporated by reference herein in their entirety.

It should be noted that while the TREF fractions in the abovedescription are obtained in a 5° C. increment, other temperatureincrements are possible. For instance, a TREF fraction could be in a 4°C. increment, a 3° C. increment, a 2° C. increment, or 1° C. increment.

For copolymers of ethylene and an α-olefin, the inventive polymerspreferably possess (1) a PDI of at least 1.3, more preferably at least1.5, at least 1.7, or at least 2.0, and most preferably at least 2.6, upto a maximum value of 5.0, more preferably up to a maximum of 3.5, andespecially up to a maximum of 2.7; (2) a heat of fusion of 90 J/g orless; (3) an ethylene content of at least 50 weight percent; (4) a glasstransition temperature, T_(g), of less than −25° C., more preferablyless than −30° C., and/or (5) one and only one T_(m).

Further, the inventive polymers can have, alone or in combination withany other properties disclosed herein, a storage modulus, G′, such thatlog(G′) is greater than or equal to 400 kPa, preferably greater than orequal to 1.0 MPa, at a temperature of 100° C. Moreover, the inventivepolymers possess a relatively flat storage modulus as a function oftemperature in the range from 0 to 100° C. (such as that illustrated inFIG. 9 and FIG. 32 that is characteristic of block copolymers, andheretofore unknown for an olefin copolymer, especially a copolymer ofethylene and one or more C₃₋₈ aliphatic α-olefins. (By the term“relatively flat” in this context is meant that log G′ (in Pascals)decreases by less than one order of magnitude between 50 and 100° C.,preferably between 0 and 100° C.).

Additionally, the ethylene/α-olefin interpolymers can have a melt index,I₂, from 0.01 to 2000 g/10 minutes, preferably from 0.01 to 1000 g/10minutes, more preferably from 0.01 to 500 g/10 minutes, and especiallyfrom 0.01 to 100 g/10 minutes. In certain embodiments, theethylene/α-olefin interpolymers have a melt index, I₂, from 0.01 to 10g/10 minutes, from 0.5 to 50 g/10 minutes, from 1 to 30 g/10 minutes,from 1 to 6 g/10 minutes or from 0.3 to 10 g/10 minutes. In certainembodiments, the melt index for the ethylene/α-olefin polymers is 1 g/10minutes, 3 g/10 minutes or 5 g/10 minutes.

The polymers can have molecular weights, M_(w), from 1,000 g/mole to5,000,000 g/mole, preferably from 1000 g/mole to 1,000,000, morepreferably from 10,000 g/mole to 500,000 g/mole, and especially from10,000 g/mole to 300,000 g/mole. The density of the inventive polymerscan be from 0.80 to 0.99 g/cm³ and preferably for ethylene containingpolymers from 0.85 g/cm³ to 0.97 g/cm³. In certain embodiments, thedensity of the ethylene/α-olefin polymers ranges from 0.860 to 0.925g/cm³ or 0.867 to 0.910 g/cm³.

The general process of making the polymers has been disclosed in thefollowing patent applications and publications: U.S. ProvisionalApplication No. 60/553,906, filed Mar. 17, 2004; U.S. ProvisionalApplication No. 60/662,937, filed Mar. 17, 2005; U.S. ProvisionalApplication No. 60/662,939, filed Mar. 17, 2005; U.S. ProvisionalApplication No. 60/566,2938, filed Mar. 17, 2005; PCT Application No.PCT/US2005/008916, filed Mar. 17, 2005; PCT Application No.PCT/US2005/008915, filed Mar. 17, 2005; PCT Application No.PCT/US2005/008917, filed Mar. 17, 2005; PCT Publication No. WO2005/090425, published Sep. 29, 2005; PCT Publication No. WO2005/090426, published Sep. 29, 2005; and, PCT Publication No. WO2005/090427, published Sep. 29, 2005, all of which are incorporated byreference herein in their entirety. For example, one such methodcomprises contacting ethylene and optionally one or more additionpolymerizable monomers other than ethylene under addition polymerizationconditions with a catalyst composition comprising:

the admixture or reaction product resulting from combining:

(A) a first olefin polymerization catalyst having a high comonomerincorporation index,

(B) a second olefin polymerization catalyst having a comonomerincorporation index less than 90 percent, preferably less than 50percent, most preferably less than 5 percent of the comonomerincorporation index of catalyst (A), and

(C) a chain shuttling agent.

Representative catalysts and chain shuttling agents are as follows.

Catalyst (A1) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195, U.S. Pat.No. 6,953,764 and No. 6,960,635, and WO 04/24740:

Catalyst (A2) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-methylphenyl)(1,2-phenylene-(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195, U.S. Pat.No. 6,953,764 and No. 6,960,635, and WO 04/24740:

Catalyst (A3) isbis[N,N′″-(2,4,6-tri(methylphenyl)amido)ethylenediamine]hafniumdibenzyl:

Catalyst (A4) isbis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)cyclohexane-1,2-diylzirconium (IV) dibenzyl, prepared substantially according to theteachings of U.S. Pat. No. 6,897,276:

Catalyst (B1) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconium dibenzyl:

Catalyst (B2) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(2-methylcyclohexyl)-immino)methyl)(2-oxoyl)zirconium dibenzyl:

Catalyst (C1) is(t-butylamido)dimethyl(3-N-pyrrolyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the techniques of U.S. Pat.No. 6,268,444:

Catalyst (C2) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings of U.S. Pat.No. 6,825,295:

Catalyst (C3) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,8a-η-s-indacen-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings of U.S. Pat.No. 6,825,295:

Catalyst (D1) is bis(dimethyldisiloxane)(indene-1-yl)zirconiumdichloride available from Sigma-Aldrich:

Shuttling Agents The shuttling agents employed include diethylzinc,di(1-butyl)zinc, di(n-hexyl)zinc, triethylaluminum, trioctylaluminum,triethylgallium, i-butylaluminum bis(dimethyl(t-butyl)siloxane),i-butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminumdi(pyridine-2-methoxide), bis(n-octadecyl)i-butylaluminum,i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminumbis(2,6-di-t-butylphenoxide, n-octylaluminum di(ethyl(1-naphthyl)amide),ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminumdi(bis(trimethylsilyl)amide), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), andethylzinc (t-butoxide).

Preferably, the foregoing process takes the form of a continuoussolution process for forming block copolymers, especially multi-blockcopolymers, preferably linear multi-block copolymers of two or moremonomers, more especially ethylene and a C₃₋₂₀ olefin or cycloolefin,and most especially ethylene and a C₄₋₂₀ α-olefin, using multiplecatalysts that are incapable of interconversion. That is, the catalystsare chemically distinct. Under continuous solution polymerizationconditions, the process is ideally suited for polymerization of mixturesof monomers at high monomer conversions. Under these polymerizationconditions, shuttling from the chain shuttling agent to the catalystbecomes advantaged compared to chain growth, and multi-block copolymers,especially linear multi-block copolymers are formed in high efficiency.

The inventive interpolymers may be differentiated from conventional,random copolymers, physical blends of polymers, and block copolymersprepared via sequential monomer addition, fluxional catalysts, anionicor cationic living polymerization techniques. In particular, compared toa random copolymer of the same monomers and monomer content, theinventive interpolymers have better (higher) heat resistance as measuredby melting point, lower compression set, particularly at elevatedtemperatures, lower stress relaxation, higher creep resistance, fastersetup due to higher crystallization (solidification) temperature, andbetter oil and filler acceptance.

The inventive interpolymers also exhibit a unique crystallization andbranching distribution relationship. That is, the inventiveinterpolymers have a relatively large difference between the tallestpeak temperature measured using CRYSTAF and DSC as a function of heat offusion, especially as compared to random copolymers containing the samemonomers and monomer level or physical blends of polymers, such as ablend of a high density polymer and a lower density copolymer, atequivalent overall density. It is believed that this unique feature ofthe inventive interpolymers is due to the unique distribution of thecomonomer in blocks within the polymer backbone. In particular, theinventive interpolymers may comprise alternating blocks of differingcomonomer content (including homopolymer blocks). The inventiveinterpolymers may also comprise a distribution in number and/or blocksize of polymer blocks of differing density or comonomer content, whichis a Schultz-Flory type of distribution. In addition, the inventiveinterpolymers also have a unique peak melting point and crystallizationtemperature profile that is substantially independent of polymerdensity, modulus, and morphology.

Polymers with highly crystalline chain ends can be selectively preparedin accordance with embodiments of the invention. In elastomerapplications, reducing the relative quantity of polymer that terminateswith an amorphous block reduces the intermolecular dilutive effect oncrystalline regions. This result can be obtained by choosing chainshuttling agents and catalysts having an appropriate response tohydrogen or other chain terminating agents. Specifically, if thecatalyst which produces highly crystalline polymer is more susceptibleto chain termination (such as by use of hydrogen) than the catalystresponsible for producing the less crystalline polymer segment (such asthrough higher comonomer incorporation, regio-error, or atactic polymerformation), then the highly crystalline polymer segments willpreferentially populate the terminal portions of the polymer. Not onlyare the resulting terminated groups crystalline, but upon termination,the highly crystalline polymer forming catalyst site is once againavailable for reinitiation of polymer formation. The initially formedpolymer is therefore another highly crystalline polymer segment.Accordingly, both ends of the resulting multi-block copolymer arepreferentially highly crystalline.

The ethylene/α-olefin interpolymers used in the embodiments of theinvention are preferably interpolymers of ethylene with at least oneC₃-C₂₀ α-olefin. Copolymers of ethylene and a C₃-C₂₀ α-olefin areespecially preferred. The interpolymers may further comprise C₄-C₁₈diolefin and/or alkenylbenzene. Suitable unsaturated comonomers usefulfor polymerizing with ethylene include, for example, ethylenicallyunsaturated monomers, conjugated or nonconjugated dienes, polyenes,alkenylbenzenes, etc. Examples of such comonomers include C₃-C₂₀α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and thelike. 1-Butene and 1-octene are especially preferred. Other suitablemonomers include styrene, halo- or alkyl-substituted styrenes,vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenics(e.g., cyclopentene, cyclohexene and cyclooctene).

While ethylene/α-olefin interpolymers are preferred polymers, otherethylene/olefin polymers may also be used. Olefins as used herein referto a family of unsaturated hydrocarbon-based compounds with at least onecarbon-carbon double bond. Depending on the selection of catalysts, anyolefin may be used in embodiments of the invention. Preferably, suitableolefins are C₃-C₂₀ aliphatic and aromatic compounds containing vinylicunsaturation, as well as cyclic compounds, such as cyclobutene,cyclopentene, dicyclopentadiene, and norbornene, including but notlimited to, norbornene substituted in the 5 and 6 position with C₁-C₂₀hydrocarbyl or cyclohydrocarbyl groups. Also included are mixtures ofsuch olefins as well as mixtures of such olefins with C₄-C₄₀ diolefincompounds.

Examples of olefin monomers include, but are not limited to propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene,4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene,vinylcyclohexane, norbornadiene, ethylidene norbornene, cyclopentene,cyclohexene, dicyclopentadiene, cyclooctene, C₄-C₄₀ dienes, includingbut not limited to 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene,1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C₄-C₄₀ α-olefins, andthe like. In certain embodiments, the α-olefin is propylene, 1-butene,1-pentene, 1-hexene, 1-octene or a combination thereof. Although anyhydrocarbon containing a vinyl group potentially may be used inembodiments of the invention, practical issues such as monomeravailability, cost, and the ability to conveniently remove unreactedmonomer from the resulting polymer may become more problematic as themolecular weight of the monomer becomes too high.

The polymerization processes described herein are well suited for theproduction of olefin polymers comprising monovinylidene aromaticmonomers including styrene, o-methyl styrene, p-methyl styrene,t-butylstyrene, and the like. In particular, interpolymers comprisingethylene and styrene can be prepared by following the teachings herein.Optionally, copolymers comprising ethylene, styrene and a C₃-C₂₀ alphaolefin, optionally comprising a C₄-C₂₀ diene, having improved propertiescan be prepared.

Suitable non-conjugated diene monomers can be a straight chain, branchedchain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms.Examples of suitable non-conjugated dienes include, but are not limitedto, straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene,1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene;3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene anddihydroocinene, single ring alicyclic dienes, such as1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ringdienes, such as tetrahydroindene, methyl tetrahydroindene,dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene,cycloalkenyl and cycloalkylidene norbornenes, such as5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene,5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene,5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene.Of the dienes typically used to prepare EPDMs, the particularlypreferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene(ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB),and dicyclopentadiene (DCPD). The especially preferred dienes are5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

One class of desirable polymers that can be made in accordance withembodiments of the invention are elastomeric interpolymers of ethylene,a C₃-C₂₀ α-olefin, especially propylene, and optionally one or morediene monomers. Preferred α-olefins for use in this embodiment of thepresent invention are designated by the formula CH₂═CHR*, where R* is alinear or branched alkyl group of from 1 to 12 carbon atoms. Examples ofsuitable α-olefins include, but are not limited to, propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and1-octene. A particularly preferred α-olefin is propylene. The propylenebased polymers are generally referred to in the art as EP or EPDMpolymers. Suitable dienes for use in preparing such polymers, especiallymulti-block EPDM type polymers include conjugated or non-conjugated,straight or branched chain-, cyclic- or polycyclic-dienes comprisingfrom 4 to 20 carbons. Preferred dienes include 1,4-pentadiene,1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene,cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferreddiene is 5-ethylidene-2-norbornene.

Because the diene containing polymers comprise alternating segments orblocks containing greater or lesser quantities of the diene (includingnone) and α-olefin (including none), the total quantity of diene andα-olefin may be reduced without loss of subsequent polymer properties.That is, because the diene and α-olefin monomers are preferentiallyincorporated into one type of block of the polymer rather than uniformlyor randomly throughout the polymer, they are more efficiently utilizedand subsequently the crosslink density of the polymer can be bettercontrolled. Such crosslinkable elastomers and the cured products haveadvantaged properties, including higher tensile strength and betterelastic recovery.

The ethylene/α-olefin interpolymers can be functionalized byincorporating at least one functional group in its polymer structure.Exemplary functional groups may include, for example, ethylenicallyunsaturated mono- and di-functional carboxylic acids, ethylenicallyunsaturated mono- and di-functional carboxylic acid anhydrides, saltsthereof and esters thereof. Such functional groups may be grafted to anethylene/α-olefin interpolymer, or may be copolymerized with ethyleneand an optional additional comonomer to form an interpolymer ofethylene, the functional comonomer and optionally other comonomer(s).Means for grafting functional groups onto polyethylene are described forexample in U.S. Pat. Nos. 4,762,890, 4,927,888, and 4,950,541, thedisclosures of these patents are incorporated herein by reference intheir entirety. One particularly useful functional group is maleicanhydride.

The amount of the functional group present in the functionalinterpolymer can vary. The functional group can typically be present ina copolymer-type functionalized interpolymer in an amount of at leastabout 1.0 weight percent, preferably at least about 5 weight percent,and more preferably at least about 7 weight percent. The functionalgroup will typically be present in a copolymer-type functionalizedinterpolymer in an amount less than about 40 weight percent, preferablyless than about 30 weight percent, and more preferably less than about25 weight percent.

More on Block Index

Random copolymers satisfy the following relationship. See P. J. Flory,Trans. Faraday Soc., 51, 848 (1955), which is incorporated by referenceherein in its entirety.

$\begin{matrix}{{\frac{1}{T_{m} -}\frac{1}{T_{m}^{0}}} = {{- \left( \frac{R}{\Delta \; H_{u}} \right)}\ln \; P}} & (1)\end{matrix}$

In Equation 1, the mole fraction of crystallizable monomers, P, isrelated to the melting temperature, T_(m), of the copolymer and themelting temperature of the pure crystallizable homopolymer, T_(m) ⁰. Theequation is similar to the relationship for the natural logarithm of themole fraction of ethylene as a function of the reciprocal of the ATREFelution temperature (° K) as shown in FIG. 3 for various homogeneouslybranched copolymers of ethylene and olefins.

As illustrated in FIG. 3, the relationship of ethylene mole fraction toATREF peak elution temperature and DSC melting temperature for varioushomogeneously branched copolymers is analogous to Flory's equation.Similarly, preparative TREF fractions of nearly all random copolymersand random copolymer blends likewise fall on this line, except for smallmolecular weight effects.

According to Flory, if P, the mole fraction of ethylene, is equal to theconditional probability that one ethylene unit will precede or followanother ethylene unit, then the polymer is random. On the other hand ifthe conditional probability that any 2 ethylene units occur sequentiallyis greater than P, then the copolymer is a block copolymer. Theremaining case where the conditional probability is less than P yieldsalternating copolymers.

The mole fraction of ethylene in random copolymers primarily determinesa specific distribution of ethylene segments whose crystallizationbehavior in turn is governed by the minimum equilibrium crystalthickness at a given temperature. Therefore, the copolymer melting andTREF crystallization temperatures of the inventive block copolymers arerelated to the magnitude of the deviation from the random relationshipin FIG. 2, and such deviation is a useful way to quantify how “blocky” agiven TREF fraction is relative to its random equivalent copolymer (orrandom equivalent TREF fraction). The term “blocky” refers to the extenta particular polymer fraction or polymer comprises blocks of polymerizedmonomers or comonomers. There are two random equivalents, onecorresponding to constant temperature and one corresponding to constantmole fraction of ethylene. These form the sides of a right triangle asshown in FIG. 2, which illustrates the definition of the block index.

In FIG. 2, the point (T_(X), P_(X)) represents a preparative TREFfraction, where the ATREF elution temperature, T_(X), and the NMRethylene mole fraction, P_(X), are measured values. The ethylene molefraction of the whole polymer, P_(AB), is also measured by NMR. The“hard segment” elution temperature and mole fraction, (T_(A), P_(A)),can be estimated or else set to that of ethylene homopolymer forethylene copolymers. The T_(AB) value corresponds to the calculatedrandom copolymer equivalent ATREF elution temperature based on themeasured P_(AB). From the measured ATREF elution temperature, T_(X), thecorresponding random ethylene mole fraction, P_(X0), can also becalculated. The square of the block index is defined to be the ratio ofthe area of the (P_(X), T_(X)) triangle and the (T_(A), P_(AB))triangle. Since the right triangles are similar, the ratio of areas isalso the squared ratio of the distances from (T_(A), P_(AB)) and (T_(X),P_(X)) to the random line. In addition, the similarity of the righttriangles means the ratio of the lengths of either of the correspondingsides can be used instead of the areas.

${BI} = \frac{{1/T_{X}} - {1/T_{XO}}}{{1/T_{A}} - {1/T_{AB}}}$ or${BI} = {- \frac{{LnP}_{X} - {LnP}_{XO}}{{LnP}_{A} - {LnP}_{AB}}}$

It should be noted that the most perfect block distribution wouldcorrespond to a whole polymer with a single eluting fraction at thepoint (T_(A), P_(AB)), because such a polymer would preserve theethylene segment distribution in the “hard segment”, yet contain all theavailable octene (presumably in runs that are nearly identical to thoseproduced by the soft segment catalyst). In most cases, the “softsegment” will not crystallize in the ATREF (or preparative TREF).

Applications and End Uses

The inventive mesophase separated ethylene/α-olefin block interpolymerscan be used in a variety of thermoplastic fabrication processes toproduce useful articles, including objects comprising at least one filmlayer, such as a monolayer film, or at least one layer in a multilayerfilm prepared by cast, blown, calendered, or extrusion coatingprocesses; molded articles, such as blow molded, injection molded, orrotomolded articles; extrusions; fibers; and woven or non-woven fabrics.The polymers may also be used in oriented film made in a double bubbleor tenter frame process. Thermoplastic compositions comprising theinventive polymers include blends with other natural or syntheticpolymers, additives, reinforcing agents, ignition resistant additives,antioxidants, stabilizers, colorants, extenders, crosslinking agents,blowing agents, and plasticizers. Of particular utility aremulti-component fibers such as core/sheath fibers, having an outersurface layer, comprising at least in part, one or more polymersaccording to embodiments of the invention. The polymers may also be usedin articles such as toys; jewelry, such as synthetic opals; and,decorative items, such as films.

They may additionally be used to form photonic crystals, photonic bandgap materials, or elastomeric optical interference films. Such materialscomprise periodic, phase-separated domains alternating in refractiveindex, with the domains sized to provide a photonic band gap in theUV-visible spectrum, such as those disclosed in U.S. Pat. No. 6,433,931,which is herein incorporated by reference.

A photonic band gap material is one that prohibits the propagation ofelectromagnetic radiation within a specified frequency range (band) incertain directions. That is, band gap materials prevent light frompropagating in certain directions with specified energies. Thisphenomenon can be thought of as the complete reflection ofelectromagnetic radiation of a particular frequency directed at thematerial in at least one direction because of the particular structuralarrangement of separate domains of the material, and refractive indicesof those domains. The structural arrangement and refractive indices ofseparate domains that make up these materials form photonic band gapsthat inhibit the propagation of light centered around a particularfrequency. (Joannopoulos, et al., “Photonic Crystals, Molding the Flowof Light”, Princeton University Press, Princeton, N.J., 1995).One-dimensional photonic band gap materials include structural andrefractive periodicity in one direction, two-dimensional photonic bandgap materials include periodicity in two directions, andthree-dimensional photonic band gap materials include periodicity inthree directions.

The reflectance and transmittance properties of a photonic crystal oroptical interference film are characterized by the optical thickness ofthe domains or regions. The optical thickness is defined as the productof the actual thickness times its refractive index. Films can bedesigned to reflect infrared, visible, or ultraviolet wavelengths oflight depending on the optical thickness of the domains.

The refractive indices of separate domains of the structures, andperiodicity in structural arrangement, are tailored to meet desiredcriteria. The periodicity in structural arrangement is met by creatingseparate domains of size similar to the wavelength (in the materialcomprising the domain as opposed to in a vacuum (freespace)) ofelectromagnetic radiation desirably effected or blocked by thestructure, preferably domains of size no greater than the wavelength ofinterest. The refractive index ratios between adjacent domains should behigh enough to establish a band gap in the material. Band gap can bediscussed with reference to the refractive index ratio (n₁/n₂), where n₁is the effective index of refraction of a first domain and n₂ is theeffective index of refraction of a second domain. In general, the largerthe refractive index ratio (refractive contrast) the larger the band gapand, in the present invention, band gap is tailored to be above apredetermined threshold and extends in one dimension for one-dimensionalsystems, two dimensions for two-dimensional systems, and threedimensions for three-dimensional systems. Suitable choices can be madeso as to tailor the refractive index profile of the adjacent domains toselectively concentrate or diffuse the optical field intensity producedby the structure. This can be accomplished in the present invention bytailoring the composition of the hard and soft blocks. The refractiveindex contrast can be further enhanced by blending components that havea preferential affinity for one type of domain. One approach is toemploy high index nanoparticle additives, such as CdSe particles, whichare coated with a surfactant layer and selectively incorporated into oneof the domains. Preferably, adjacent, dissimilar domains or segmentshaving a difference in mole percent α-olefin content differ inrefractive index such that the ratio of the refractive index of one tothe other is greater than 1, preferably at least about 1.01, and morepreferably at least about 1.02 for a continuous set of wavelengths lyingwithin a wavelength range of from about 100 nm to about 10 μm. In someembodiments, the refractive index ratio is from 1.00 to 1.10, preferably1.01 to 1.06 and more preferably 1.02 to 1.05 for a continuous set ofwavelengths lying within a wavelength range of from about 100 nm toabout 10 μm. According to another set of embodiments, these preferredrefractive index ratios exist for a continuous set of wavelengths lyingwithin a wavelength range of from about 300 nm to about 700 nm, andaccording to another set of embodiments, the ratio of refractive indexof one to the other is at least 1.0 or is from 1.00 to 1.10, preferably1.01 to 1.06 and more preferably 1.02 to 1.05 for a continuous set ofwavelengths lying within a wavelength range of from about 400 nm to 50μm. These dielectric structures, exhibiting a band gap in theirdispersion relation, cannot support electromagnetic waves at certainfrequencies thus those waves are inhibited from propagating through thematerial.

The polymeric structure should be made of material that, in adisarranged state (not arranged with the periodic structure necessaryfor photonic band gap properties) is at least partially transparent tothe electromagnetic radiation of interest. When the material is at leastpartially transparent to the electromagnetic radiation of interest,defects in the ordered domain structure of the photonic band gapmaterial define pathways through which the electromagnetic radiation canpass since the criteria for blocking the radiation is destroyed.

In certain compositions, one or more of the blocks or segments iscrystalline or semicrystalline. This crystallinity is one distinguishingfeature of the inventive interpolymers compared to materials of theprior art that have been used as photonic materials. This crystallinityprovides a mechanism whereby the photonic behavior can be reversiblyturned on or off, particularly when one block or segment is crystallineand the other block type is amorphous. For example, the refractive indexof molten semicrystalline polyethylene is the same as that of anamorphous ethylene/1-octene interpolymer. Such materials can be heatedabove their melting temperature, where they lose the refractive indexcontrast necessary to exhibit characteristics of a photonic crystal.However, upon cooling, the semicrystalline material crystallizes andrestores the refractive index contrast and resulting photonicproperties.

Size of the domains is another important parameter affecting thephotonic properties of the material. Domain size can be varied byselecting the relative molecular weights and compositions of the variousblocks. Additionally, a diluent (compatible solvent, homopolymer, etc.)can be used to swell all the domains, or in other cases selectivelyswell an individual type of domain.

In some embodiments, the long range order and orientation of the domainscan be affected by processing techniques. One such processing techniqueinvolves treating a homogeneously mixed spun cast film by bringing itabove the highest glass transition temperature (T_(g)) or meltingtemperature (T_(m)) of the components for a time sufficient to producethe desired ordered mesophase separated morphology. The resultingmorphology will take the form of the components separating intomesodomains with shapes that, for example, can be cylindrical orrodlike, spherical, bicontinuous cubic, lamellar or otherwise. The filmmay be brought above the T_(g) or T_(m) of the components by heating or,for example, by the use of a solvent which lowers the transitiontemperature of the components below the room or ambient temperature ofthe operating environment. Prior to treating, the copolymer will be in athermodynamically unstable single phase which, when brought above theT_(g) or T_(m) of its components will separate into the mesodomains. Incertain instances, the mesophase separation in AB block copolymers willyield stacked lamella consisting of alternating A and B slabs or layerswith different refractive indices. In addition, if such copolymers areroll cast from solution, then well ordered, globally orientedmesodomains can be formed. Other known methods of globally orientinglamellar films are the use of surface-induced ordering, mechanical, suchas shear, alignment, biaxial orientation, and electric field or magneticfield alignment.

Other embodiments of the invention do not require spin or roll castingto achieve the desired ordered structure. For example, simplecompression molding of the inventive polymers can provide a film thatdisplays photonic properties, thus providing a tremendous advantage interms of processing costs. Other typical melt processing techniques,such as injection molding, blown or cast film processing, profileextrusion, drawn or blown fiber formation, calendaring and otherconventional polymer melt processing techniques, may be used to achievesimilar affects.

Some examples of the films exhibit iridescence and changing colors asthe angle of incident light on the film is changed.

The inventive block interpolymers can also be fabricated to formmechanochromic films. A mechanochromic films is a material whichresponds to deformation by changing color. In these materials, thewavelength reflected changes reversibly with the applied strain due tothe change in optical thickness. As the film is stretched, the change inthe thickness of the layers causes the film to reflect differentwavelengths of light. As the film is relaxed, the layers return to theiroriginal thickness and reflect their original wavelengths. In some casesthe reflectivity can be tailored from the visible through nearinfraredregimes with applied stress.

The inventive block interpolymers may also be used to form polymericreflective bodies for infrared, visible, or ultraviolet light, asdescribed in U.S. Pat. No. 3,711,176, which is herein incorporated byreference. This patent describes materials that are formed by extrusionof multiple polymeric materials to create ordered layered structureswith layers on the 50-1000 nm scale. The inventive interpolymers areadvantaged over these materials because they do not require theexpensive and tedious processing techniques, namely microlayerextrusion, to form the reflective bodies.

The optical interference films of the inventive block interpolymers mayalso be useful in a variety of optical applications such as Fresnellenses, light pipes, diffusers, polarizers, thermal mirrors, diffractiongratings, band-pass filters, optical switches, optical filters, photonicbandgap fibers, optical waveguides, omnidirectional reflectors,brightness-enhancement filters, and the like.

The transparent elastomeric optical interference films of the presentinvention have a number of uses. Such materials can be used in windowfilms, lighting applications, pressure sensors, privacy filters, eyeprotection, colored displays, UV-protective tapes, greenhouse films,packaging, toys and novelty items, decorative, and securityapplications. For example, the films may be used for packaging whichdisplay changing color patterns. The wrapping of irregular shaped itemswill cause the films to stretch in a variety of ways and exhibit uniquecolor patterns. Toy or novelty items which change colors when stretched,such as balloons or embossed patterns are also possible. Pulsating signsor advertisements may be fabricated in which selective stretching ofportions of the film by an inflation/deflation mechanism causes apulsating color change effect.

The optical interference films of the present invention may also finduse as solar screens which reflect infrared light. In films with varyingthickness of the domains, the film can be made to reflect a broad bandwidth of light. Because of the elasticity of the films, the infraredreflecting characteristics of the film may be changed by stretching thefilms. Thus, depending upon the desired characteristics, the film can bemade to reflect infrared during certain times of the day, and then bestretched to appear transparent to visible light. Even when stretched,the film will continue to reflect ultraviolet wavelengths.

The elastomeric films of the present invention may also be used asadjustable light filters in photography by stretching the film to causeit to reflect different wavelengths of light. The films of the presentinvention may also find use in agriculture. As it is known that plantgrowth is influenced by the wavelength of light received by the plant, agreenhouse film may be formed that varies the transmitted wavelengths oflight desired. Further, if transmission of a specific wavelength oflight is desired as the angle of incidence of sunlight changes duringthe day, the film may be adjusted by stretching or relaxing it tomaintain a constant transmitted wavelength.

The films of the present invention may also be used as pressure sensorsto detect pressure changes and exhibit a color change in responsethereto. For example, the film of the present invention may befabricated into a diaphragm or affixed to another rubbery surface suchas that of a tire to act as a pressure or inflation sensor. Thus, anelastomeric film sensor may be provided which, for example, reflects redwhen an under-inflated condition is encountered, green when there is acorrect pressure, and blue when there exists an over-inflated condition.

Elastomeric films of the present invention may also find use as straingauges or stress coatings. A film of the present invention may belaminated to the surface of a structure, and then exposed to a load.Deformation of the surface may then be measured precisely using aspectrophotometer which measures the change in wavelength of lightreflected from the film. Extremely large surface areas may be coveredwith the film of the present invention.

Elastomeric films of the present invention are useful in coloreddisplays, such as described in U.S. Pat. No. 7,138,173, which isincorporated herein in its entirety by reference. Such displays arefrequently used as a means to display information in an eye-catchingmanner, or to draw attention to a specific article on display or forsale. These displays are often used in signage (e.g., outdoor billboardsand street signs), in kiosks, and on a wide variety of packagingmaterials. It is particularly advantageous if a display can be made tochange color as a function of viewing angle. Such displays, known as“color shifting displays”, are noticeable even when viewed peripherally,and serve to direct the viewer's attention to the object on display.

Backlit displays having a variety of optical arrangements may be madeusing the films of the present invention. The actual device need notnecessarily be a display, but could be a luminaire or a light sourcewhich uses the combination of film spectral-angular properties andwavelength emission from a lamp to create a desired light distributionpattern. This recycling, coupled with the high reflectivity of thefilms, produces a much brighter color display than is seen withconventional displays.

The films of the present invention may be used in conjunction with adistributed light source or several point sources, just as conventionalbacklights are now used for advertising signs or computer backlights. Aflat reflective film, uniformly colored by optical interference, whichcovers the open face of a backlight will change color as the viewerpasses by the sign. Opaque or translucent lettering of a chosen dyed orpigmented color can be applied to the reflective cover film via laser orscreen printing techniques. Alternatively, interference reflectivelettering composed of a different colored reflective film than the coverfilm can also be applied over cutouts made in the cover film, with thelettering displaying the opposite change in color from the cover film,e.g., cover film displays a green to magenta change with angle, whilethe lettering shows a magenta to green change over the same angles. Manyother color combinations are possible as well.

The color changes in the cover film can also be used to “reveal”lettering, messages, or even objects that are not visible through thefilm at large angles of incidence, but become highly visible when viewedat normal incidence, or vice-versa. This “reveal” effect can beaccomplished using specific color emitting lights in the backlight, orby dyed colored lettering or objects under the reflective cover film.

The brightness of the display can be enhanced by lining the inside ofthe backlight cavity with highly reflective interference film. In thissame manner, the overall color balance of the display can be controlledby lining a low reflectance cavity with a reflective film thatpreferentially reflects only certain colors. The brightness of thechosen color may suffer in this case because of its transmission atcertain angles through the lining. If this is undesirable, the desiredcolor balance can be effected by coating a broadband liner film with adye of the appropriate color and absorbance.

The reflective colored film may also be used in combination with dyed orpigment colored films with the latter on the viewer side to achieve adesired color control such as, e.g., eliminating a color shift on thelettering while producing a color shifting background.

The backlit sign need not be planar, and the colored film could beapplied to more than one face of the sign, such as an illuminated cube,or a two sided advertising display.

The films of the present invention may also be used to create a varietyof non-backlit displays. In these displays, at least one polarization oflight from an external light source, which may be sunlight, ambientlighting, or a dedicated light source, is made to pass through theinterference film twice before the transmission spectrum is seen by theviewer. In most applications, this is accomplished by using theinterference film in combination with a reflective or polarizingsurface. Such a surface may be, for example, a conventional mirror ofthe type formed through deposition of metals, a polished metal ordielectric substrate, or a polymeric mirror or polarizing film.

While the interference films of the present invention may be usedadvantageously in combination with either specularly reflective ordiffusely reflective surfaces, a diffusely reflecting substrate ispreferred. Such a substrate causes the colors transmitted by the film(and subsequently reflected by the substrate) to be directed out of theplane of incidence, or at a different angle of reflection in the planeof incidence, than the colored light that is specularly reflected by thefilm thereby allowing the viewer to discriminate between the transmittedand reflected colors. Diffuse white surfaces, such as card stock orsurfaces treated with a diffusely reflective white paint, are especiallyadvantageous in that they will create a display that changes color withangle.

In other embodiments, the diffuse surface, or portions thereof, maythemselves be colored. For example, a diffuse surface containing inkcharacters may be laminated with a interference film that has at leastone optical stack tuned to reflect light over the same region of thespectrum over which the ink absorbs. The characters in the resultingarticle will then be invisible at certain angles of viewing but clearlyvisible at other angles (a similar technique may be used for backlitdisplays by matching the reflective bandwidth of the interference filmto the absorption band of the ink). In still other embodiments, theinterference film itself can be printed on with a diffuse white orcolored ink, which may be either opaque or translucent. Translucent isdefined in this context as meaning substantially transmissive with asubstantial diffusing effect. Alternatively, the interference film canbe laminated to a white or colored surface, which can itself also beprinted on.

In still other embodiments, the films of the invention may be used incombination with a substrate that absorbs the wavelengths transmitted bythe film, thereby allowing the color of the display to be controlledsolely by the reflectivity spectrum of the film. Such an effect isobserved, for example, when a colored mirror film of the presentinvention, which transmits certain wavelengths in the visible region ofthe spectrum and reflects other wavelengths in the visible region, isused in combination with a black substrate.

The optical films and devices of the present invention are suitable foruse in fenestrations, such as skylights or privacy windows. In suchapplications, the optical films of the present invention may be used inconjunction with, or as components in, conventional glazing materialssuch as plastic or glass. Glazing materials prepared in this manner canbe made to be polarization specific, so that the fenestration isessentially transparent to a first polarization of light butsubstantially reflects a second polarization of light, therebyeliminating or reducing glare. The physical properties of the opticalfilms can also be modified as taught herein so that the glazingmaterials will reflect light of one or both polarizations within acertain region of the spectrum (e.g., the UV region), while transmittinglight of one or both polarizations in another region (e.g., the visibleregion). This is particularly important in greenhouse applications,where reflection and transmission of specific wavelengths can beutilized to control plant growth, flowering, and other biologicalprocesses.

The optical films of the present invention may also be used to providedecorative fenestrations which transmit light of specific wavelengths.Such fenestrations may be used, for example, to impart a specific coloror colors to a room (e.g., blue or gold), or may be used to accent thedecor thereof, as through the use of wavelength specific lightingpanels.

The optical films of the present invention may be incorporated intoglazing materials in various manners as are known to the art, as throughcoating or extrusion. Thus, in one embodiment, the optical films areadhered to all, or a portion, of the outside surface of a glazingmaterial, for example, by lamination with the use of an opticaladhesive. In another embodiment, the optical films of the presentinvention are sandwiched between two panes of glass or plastic, and theresulting composite is incorporated into a fenestration. Of course, theoptical film may be given any additional layers or coatings (e.g., UVabsorbing layers, antifogging layers, or antireflective layers) torender it more suitable for the specific application to which it isdirected.

One particularly advantageous use of the colored films of the presentinvention in fenestrations is their application to sunlit windows, wherereversible coloring is observed for day vs. night. During the day, thecolor of such a window is dictated primarily by the transmissiveproperties of the film toward sunlight. At night, however, very littlelight is seen in transmission through the films, and the color of thefilms is then determined by the reflectivity of the film toward thelight sources used to illuminate the room. For light sources whichsimulate daylight, the result is the complimentary color of the filmappearance during the day.

The films of the present invention may be used in various light fixtureapplications, including the backlit and non-backlit displays describedearlier. Depending on the desired application, the film may be uniformlycolored or iridescent in appearance, and the spectral selectivity can bealtered to transmit or reflect over the desired wavelength range.Furthermore, the film can be made to reflect or transmit light of onlyone polarization for polarized lighting applications such as polarizedoffice task lights or polarized displays incorporating light recyclingto increase brightness, or the film can be made to transmit or reflectboth polarizations of light when used in applications where coloredmirrors or filters are desirable.

In the simplest case, the film of the present invention is used as afilter in a backlit light fixture. A typical fixture contains a housingwith a light source and may include a diffuse or specular reflectiveelement behind the light source or covering at least some of theinterior surfaces of the optical cavity. The output of the light fixturetypically contains a filter or diffusing element that obscures the lightsource from direct viewing. Depending upon the particular application towhich the light fixture is directed, the light source may be afluorescent lamp, an incandescent lamp, a solid-state orelectroluminescent (EL) light source, a metal halide lamp, or even solarillumination, the latter being transmitted to the optical cavity by freespace propagation, a lens system, a light pipe, a polarizationpreserving light guide, or by other means as are known to the art. Thesource may be diffuse or specular, and may include a randomizing,depolarizing surface used in combination with a point light source. Theelements of the light fixture may be arranged in various configurationsand may be placed within a housing as dictated by aesthetic and/orfunctional considerations. Such fixtures are common in architecturallighting, stage lighting, outdoor lighting, backlit displays and signs,and automotive dashboards. The film of the present invention providesthe advantage that the appearance of the output of the lighting fixturechanges with angle.

The color shifting films of the present invention are particularlyadvantageous when used in directional lighting. High efficiency lamps,such as sodium vapor lamps commonly used in street or yard lightingapplications, typically have spectral emissions at only one majorwavelength. When such a source which emits over a narrow band iscombined with the film of the present invention, highly directionalcontrol of the emitted light can be achieved. For example, when theinventive film is made with a narrow passband which coincides with theemission peak of the lamp, then the lamp emission can pass through thefilm only at angles near the design angle; at other angles, the lightemitted from the source is returned to the lamp, or lamp housing.Typical monochromatic and polychromatic spikey light sources include lowpressure sodium lamps, mercury lamps, fluorescent lamps, compactfluorescent lamps, and cold cathode fluorescent lamps. Additionally, thereflecting film need not necessarily be of a narrow pass type since,with monochromatic sources, it may only be necessary to block or passthe single wavelength emission at a specific angle of incidence. Thismeans that a reflective film having, for example, a square wavereflection spectrum which cuts on or off at a wavelength near that ofthe lamp emission can be used as well. Some specific geometries in whichthe light source and film of the present invention can be combinedinclude, but are not limited to, the following:

-   -   (a) A cylindrical bulb, such as a fluorescent tube, is wrapped        with film designed for normal incidence transmission of the        bulb's peak emitted radiation, i.e., the film is designed with a        passband centered at the wavelength of the lamp emission. In        this geometry, light of the peak wavelength is emitted mainly in        a radial direction from the bulb's long axis;    -   (b) An arbitrary bulb geometry in a reflective lamp housing can        be made to radiate in a direction normal to the plane of the        housing opening by covering the opening with a film selected to        transmit at the bulb's peak emitted radiation. The opening can        face downward or in any other direction, and the light will be        viewable at angles in a direction normal to the plane of the        opening but not at angles of incidence substantially away from        normal;    -   (c) Alternately, the combination described in (b) can use a film        that is designed to transmit the lamp emission at one or more        angles of incidence away from the normal angle by providing one        or more appropriate passbands, measured at normal incidence, at        wavelengths greater than the lamp emission wavelength. In this        way, the lamp emission is transmitted at angles where the blue        shift of the passband is sufficient to align the emission peak        with the passband;    -   (d) Combining the angular distribution film described in (c)        with the geometry described in (a) will give a cylindrical bulb        in which one can have direction control of the emitted light in        a plane parallel to the long axis of the bulb; or    -   (e) A polychromatic spikey light source, for example, one having        emission spikes at three different wavelengths, can be combined        with an inventive film having only one passband, and such that        the film transmits only one of the three color spikes at a given        angle of incidence and each emission peak is transmitted at a        different angle. Such a film can be made using multiple groups        of layers, each of which reflect at different wavelength        regions, or it can be made using one group of layers and their        higher order harmonics. The width of the first order bandwidth        region and consequently the width of the harmonic bandwidths,        can be controlled to give desired transmission gaps between the        first order and harmonic reflection bands. The combination of        this film with the polychromatic spikey light source would        appear to split light from an apparently “white” light source        into its separate colors.

Since the rate of spectral shift with angle is small near normalincidence, the angular control of light is less effective at normalincidence compared to high angles of incidence on the inventive film.For example, depending on the width of the lamp emission lines, and thebandwidth of the passband, the minimum angular control may be as smallas +/−10 degrees about the normal, or as great as +/−20 degrees or +/−30degrees. Of course, for single line emitting lamps, there is no maximumangle control limit. It may be desirable, for either aesthetic or energyconservation reasons, to limit the angular distribution to angles lessthan the free space available to the lamp, which is typically +/−90degrees in one or both of the horizontal and vertical planes. Forexample, depending on customer requirements, one may wish to reduce theangular range to +/−45, +/−60 or only +/−75 degrees. At high angles ofincidence, such as 45 degrees or 60 degrees to the normal of the film,angular control is much more effective. In other words, at these angles,the passband shifts to the blue at a higher rate of nm/degree than itdoes at normal incidence. Thus, at these angles, angular control of anarrow emission peak can be maintained to within a few degrees, such as+/−5 degrees, or for very narrow passbands and narrow emission lines, toas small as +/−2 degrees.

The films of the present invention can also be shaped in a pre-designedfashion to control the angular out put of the lamp in the desiredpattern. For example, all or part of the film placed near the lightsource may be shaped to corrugated or triangular waveforms, such thatthe axis of the waveform is either parallel or perpendicular to the axisof the lamp tube. Directional control of different angles in orthogonalplanes is possible with such configurations.

While the combination of a narrow band source and an inventive filmworks well to control the angle at which light is emitted or detected,there are only a limited number of sources with narrow emission spectraand therefore limited color options available. Alternately, a broadbandsource can be made to act like a narrow band source to achieve similardirectional control of the emitted light. A broadband source can becovered by a color selective film that transmits in certain narrow bandwavelength regions, and that modified source can then be used incombination with a second film having the same transmission spectrum sothat the light emitted from the source/color selective film combinationcan again pass through the inventive film only at the design angle. Thisarrangement will work for more than one color, such as with a threecolor red-green-blue system. By proper selection of the films, theemitted colors will be transmitted at the desired angle. At otherangles, the emitted wavelengths will not match every or any passband,and the light source will appear dark or a different color. Since thecolor shifting films can be adapted to transmit over a broad range ofwavelengths, one can obtain virtually any color and control the angulardirection over which the emitted light is observed.

Direction dependent light sources have utility in many applications. Forexample, the light sources of the present invention can be used forilluminating automobile instrument panels so that the driver, who isviewing the instruments at a normal angle, can view the transmittedlight, but the light would not be reflected off the windshield orviewable by a passenger because they would be at off angles to theinstruments. Similarly, illuminated signs or targets can be constructedusing the direction dependent light sources of the present invention sothat they can be perceived only at certain angles, for example, normalto the target or sign, but not at other angles. Alternately, the filmcan be designed so that light of one color is transmitted at one angle,but a different color is detectable at another angle. This would beuseful, for example, in directing the approach and stopping point forvehicles, such as for a carwash or emission check station. Thecombination of inventive film and light source can be selected so that,as a vehicle approached the illuminated sign and the driver was viewingthe film at non-normal angles to the sign, only green light would bevisible, but the perceived transmitted light would shift to red at theangle where the vehicle was to stop, for example, normal to the sign.The combination of the inventive film and a narrow band source is alsouseful as a security device, wherein the film is used as a securitylaminate, and a light source wrapped with the same film is used as asimple verification device. Other examples of the direction dependentlight source of the present invention are described in more detail inthe following examples.

Spectrally selective films and other optical bodies can be made inaccordance with the teachings of the present invention which are ideallysuited for applications such as horticulture. A primary concern for thegrowth of plants in greenhouse environments and agriculturalapplications is that of adequate levels and wavelengths of lightappropriate for plant growth. Insufficient or uneven illumination canresult in uneven growth or underdeveloped plants. Light levels that aretoo high can excessively heat the soil and damage plants. Managing theheat generated by ambient solar light is a common problem, especially insouthern climates.

The spectrally selective color films and optical bodies of the presentinvention can be used in many horticultural applications where it isdesired to filter out or transmit specific wavelengths of light that areoptimal for controlled plant growth. For example, a film can beoptimized to filter out heat producing infrared and non-efficientvisible solar wavelengths in order to deliver the most efficientwavelengths used in photosynthesis to speed plant growth and to managesoil and ambient temperatures.

It is known that plants respond to different wavelengths duringdifferent parts of their growth cycle. Throughout the growth cycle, thewavelengths in the 500-580 nm range are largely inefficient, whilewavelengths in the 400-500 nm and 580-800 nm ranges illicit a growthresponse. Similarly, plants are insensitive to IR wavelengths past about800 nm, which comprise a significant part of solar emission, so removalof these wavelengths from the solar spectrum can significantly reduceheating and allow for concentration of additional light at wavelengthsuseful for plant growth.

Commercial lamps used in greenhouses are effective in acceleratingphotosynthesis and other photoresponses of plants. Such lamps are mostcommonly used as supplements to natural, unfiltered solar light. Lampsthat emit energy in the blue (about 400-500 nm), red (about 600-700 nm),or near IR (about 700-800 nm) are used in accelerating growth. Onecommon commercial grow-lamp has its emission maxima at 450 and 660 nm,with little emission of wavelengths beyond 700 nm. Another common sourcehas high emission in the blue and red, and high emission in the near IRwavelengths. Lamps which emit wavelengths in the range of 500-580 nm arereferred to as “safe lights” because their emission is in a low responseregion and does not significantly affect plant growth, eitherbeneficially or detrimentally.

Light sources used in general lighting are often paired to accomplishsimilar results to the “grow lights”. The output wavelengths from somesources actually retard growth, but this can be compensated for bypairing with other sources. For example, low pressure sodium used alonecan inhibit synthesis of chlorophyll but when the low pressure sodium iscombined with fluorescent or incandescent lamps, normal photosynthesisoccurs. Examples of common pairings of commercial lights used ingreenhouses include (i) high pressure sodium and metal halide lamps;(ii) high pressure sodium and mercury lamps; (iii) low pressure sodiumand fluorescent and incandescent lamps; and (iv) metal halide andincandescent lamps.

In a greenhouse environment, the color selective films and opticalbodies of the present invention, when used alone as color filters or incombination with reflective backings, are useful for concentrating lightof the desired wavelengths for optimal plant growth. The films andoptical bodies may be used with normal unfiltered solar light, or theymay be combined with artificial broadband light sources to control thewavelength of light emitted from the source. Such light sources include,but are not limited to, incandescent lamps, fluorescent lamps such ashot or cold cathode lamps, metal halide lamps, mercury vapor lamps, highand low pressure sodium lamps, solid-state or electroluminescent (EL)lights, or natural or filtered solar light that is optically coupled tothe color selective film. Several filtration/concentration systems willbe described in more detail that may be used to manage heat in thegreenhouse environment, while delivering an increased amount of light atwavelengths optimized for photosynthesis and other plant photoresponses.

The interference films and optical bodies of the present invention canalso be used with one or more direct or pre-filtered artificial lightsources so as to optimize the spectra afforded by these films evenfurther. In some cases, it may be desirable to wrap or otherwise couplethe interference film directly to the artificial source so that ineffect the light source emits primarily the wavelengths desired forcontrolled plant growth. The film may also be laminated directly to theclear panels which make up the roof and/or walls of a typical greenhouseso that much of the light that enters the building is of the desiredspectral composition, or else such panels may be extruded to include oneor more color selective films within the panel itself. In order that allof the light entering the building would be of a precise wavelengthrange, it would be desirable to have the films mounted on a heliostat orother mechanism that moves to compensate for the angle of the sun's raythroughout the day. Simpler mechanisms such as south facing panels withonly a weekly or monthly change in the angle from the horizontal orvertical can perform quite well also.

One or more reflectors can also be used to direct the filtered light todesired locations, and it is understood that various physical shapes ofthe deflector and/or interference film can be used to aim or spreadlight across desired portions of the room. In addition to thesedescribed modes of use, the film can be used as a filtered wrapping forindividual plants, as a reflector placed between plants and soil eitherin film form or as slit or chopped mulch, or as reflectors and filtersfor use in aquarium lighting for aquatic plants.

In addition to the previously described spectrally selective films thatcan be tailored to transmit or reflect infrared and/or green light thatis not useful for plant growth, a film designed to control the amount ofred light, typically from about 660-680 nm, and the amount of far redlight, typically from about 700-740 nm, is especially useful to controlplant growth. It has been shown that the ratio of red to far red lightshould be maintained at a level of 1.1 or higher in order to reduceelongation and force plants to branch or propagate, resulting inthicker, denser plant growth. Additionally, by precisely controlling thered/far red ratio and the sequencing of wavelength exposure, many plantscan be forced into a flowering state or held in the vegetative state.Some plant varieties can be controlled with as little as 1 minute of redor far red doping. Plant responses to red and far red light have beendescribed in J. W. Braun, et al., “Distribution of Foliage and Fruit inAssociation with Light Microclimate in the Red Raspberry Canopy, 64(5)Journal of Horticultural Science 565-72 (1989) and in Theo J. Blow, “NewDevelopments in Easter Lilly Height Control” (Hort. Re. Instit. OfOntario, Vineland Station, Ont. LOR 2EO.

Previous attempts to control the red/far red ratio have utilized lightblocking liquids that are pumped into the cavity between panes ingreenhouse twin wall constructions. This has not been satisfactorybecause of the difficulty in adding and removing the liquid. Otherattempts have been made to use colored film for the roof glazing, but itis difficult to control if the plant variety in the greenhouse changesfrequently or if outdoor weather conditions change. The film of thepresent invention is ideally suited for this application. The red/farred ratio can be controlled by varying the thickness gradient or bychanging the angle of the film to permit the desired wavelengths toreach the plants. To compensate for varying outdoor conditions orvarying needs of different plant varieties, the film is preferablypositioned within the greenhouse in such a way that it can be eitherused or stored, for example, by a rolling shade along the roof linewhich can be drawn down or rolled up, or by a shade cloth pulledhorizontally above the plant height. Alternately, individual enclosuresof the film can be constructed for separate plants or groups of plants.

The film of the present invention can also be used in conjunction withconventional mirrors to control the intensity of any desired portion ofthe sunlight spectrum that reaches the plants. Generally, it isdesirable to expose plants to a constant level of the wavelengths andintensity of light useful for plant growth throughout the entire day. Ona typical sunny day, however, the light level peaks at about noon, andthis light level may be excessive for many plants; the leaf temperatureoften rises, which decreases the plant efficiency. It is preferable toreduce the level of light reaching the plant during mid-day to provide amore uniform level throughout the day. For example, roses flower mostefficiently when exposed to a maximum light level of 600 μmol/sec-m²,and this level is often achieved by 11:00 am during the winter months ata latitude of 45 degrees. Reducing the light level between 11:00 and1:00 improves the plant yield. The combined usage of conventionalmirrors with our wavelength selective films can be used to change theintensity of light directed to plants during different hours of the day.For example, the use of a visible mirror can be discontinued during thehours of highest solar incidence by redirecting its angle of reflectionto reject that portion of light from the sun. Other combinations ofbaffles and curtains can also be used with our wavelength selectivefilms to control the intensity of light.

Counterfeiting and forgery of documents and components, and the illegaldiversion of controlled materials such as explosives, is a serious andpervasive problem. For example, commercial aircraft maintenance crewsregularly encounter suspected counterfeit parts, but lack a reliablemeans to distinguish between high-grade parts and counterfeit parts thatare marked as meeting specifications. Similarly, it is reported that upto ten percent of all laser printer cartridges that are sold as new areactually refurbished cartridges that have been repackaged andrepresented as new. Identification and tracking of bulk items such asammonium nitrate fertilizer usable in explosives is also highlydesirable, but current means of identification are prohibitivelyexpensive.

Several means exist to verify the authenticity of an item, the integrityof packaging, or to trace the origin of parts, components, and rawmaterials. Some of these devices are ambient verifiable, some areverifiable with separate lights, instruments, etc., and some combineaspects of both. Examples of devices used for the verification ofdocuments and package integrity include iridescent inks and pigments,special fibers and watermarks, magnetic inks and coatings, fineprintings, holograms, and Confirm® imaged retroreflective sheetingavailable from 3M. Fewer options are available for authentication ofcomponents, mostly due to size, cost, and durability constraints.Proposed systems include magnetic films and integrated circuit chips.

Microtaggants have been used to trace controlled materials such asexplosives. These materials are typically multilayer polymers that areground up and dispersed into the product. The individual layers in themicrotaggant can be decoded using an optical microscope to yieldinformation pertaining to the date and location of manufacture. Therehas been a long unmet need for a security film product that is bothambient verifiable and machine readable, that is manufacturable but noteasily duplicated, that is flexible and can be used on a variety of partsizes ranging from near microscopic to large sheets, and that may becoded with specific, machine-readable information.

The films and optical bodies of the present invention can be tailored toprovide a security film or device useful as a backing, label, oroverlaminate that meets all of these needs. The color shifting featureand high reflectivity and color saturation at oblique angles areproperties that can be exploited to uniquely identify a document orpackage, and spectral detail can be designed into the films to provideunique spectral fingerprints that may be used to identify specific lotsof security film to code individual applications. The security films andoptical bodies can be tailored to reflect over any desired portion ofthe spectrum, including visible, infrared, or ultraviolet. When onlycovert identification is desired, a film can be made that appearstransparent in the visible region of the spectrum but that has varyingtransmission and reflections bands in the infrared region to impart acovert spectral fingerprint.

Information can also be encoded in the security films and optical bodiesof the present invention by several other methods, either alone or incombination with the above described methods of varying the intensityand position of transmission and reflection bands. For example,individual layers may be tuned to the infrared portion of the spectrum,and overtones in the visible region can be controlled to produce uniquespectra.

The spectrally selective security films and optical bodies of thepresent invention may also include relatively thick layers either withinthe optical stack or adjacent to the optical stack, and these layers mayalso be used to impart information that can be decoded by opticalinspection of a cross-section of the film. The films may also becombined with colored printing or graphics printed on a substrate belowthe film to provide indicia that may be hidden or viewable depending onthe angle of observation. Color contrast may be achieved by thinning theoptical layers locally. Within this affected region, a new color thatalso color shifts is evident against the unaffected region. To affect alocalized thinning of layers, the preferred method is embossing attemperatures above the glass transition temperatures of all of thepolymers in the film and/or with suitable pressure. Localized thinningof layers could also be achieved by bombardment with high energyparticles, ultrasonics, thermoforming, laser pulsing and stretching. Aswith the other color selective films already described, the securityfilm may incorporate a hardcoat, an antireflective surface, or anabsorbing coating to improve durability and contrast. The security filmsmay also incorporate a heat activated or pressure sensitive adhesive tofunction as a label or die-cut.

For most applications, the security films or other optical bodies of thepresent invention can be appropriately sized and laminated directly to adocument or packaging material. The spectral features of these films aretypically very narrow to reflect the minimum amount of light. While thespectral features of the film will typically be limited to the infraredso as not to occlude the document or package, the character and color ofthe film may also be used to enhance the appearance of the article.

For some applications, the security film may be used in a bulk materialby grinding the film into a powder and dispersing the powder into thematerial. Paints, coatings and inks can be formulated from ground upplatelets utilizing the films of this invention. In cases where the bulkmaterial may be an explosive, it may be desirable to avoid usingoriented material if substantial relaxation would occur during anexplosion. Optionally, the powder may be coated with an ablativematerial such as an acrylate to absorb energy during an explosive event.

The security films and optical bodies of the present invention may beread by a combination of ambient verification (for example, the presenceof a colored, reflective film on an article, possibly combined withidentifiable performance at non-normal angles) and instrumentverification. A simple machine reader may be constructed using aspectrophotometer. Several low cost spectrophotometers based on CCDdetector arrays are available which meet the needs of this invention;preferably, these include a sensor head connected to thespectrophotometer with a fiber optic cable. The spectrophotometer isused to determine the spectral code of the film by measuring lightincident on the article at a predetermined angle or angles, which can benormal to the film at oblique angles, or a combination of both.

In addition to exploiting the optical properties of the films of thepresent invention for security applications, the mechanical propertiesof these films can also be utilized. Thus, for example, the films of thepresent invention can be intentionally designed to have low resistanceto interlayer delamination, thereby providing anti-tamperingcapabilities.

As noted elsewhere herein, the color shifting properties of the films ofthe present invention may be used advantageously in numerous decorativeapplications. Thus, for example, the films of the present invention maybe used, either alone or in combination with other materials, films,substrates, coatings, or treatments, to make wrapping paper, gift paper,gift bags, ribbons, bows, flowers, and other decorative articles. Inthese applications, the film may be used as is or may be wrinkled, cut,embossed, converted into glitter, or otherwise treated to produce adesired optical effect or to give the film volume.

The optical interference film of the present invention may alsooptionally include a skin layer on one or both major surfaces of thefilm. The skin layer comprises a blend of a substantially transparentelastomeric polymeric material with a substantially transparent,nonelastomeric polymeric material having substantially the same index ofrefraction as the elastomeric polymer. Optionally, the elastomericpolymeric material in the skin layer may be one of the elastomers whichmakes up the alternating layer of the optical interference film. Inpreferred examples, the skin layer retains elastomeric characteristicsand transparency while providing the film with a protective surfacewhich is nonblocking. The skin layer also remains receptive tolamination of the film to other surfaces as well as receptive to inks orother forms of printing.

Microporous Films

The inventive copolymers can also be used to form microporous polymericfilms, which have use in many applications such as clothing, shoes,filters, and battery separators, as described in US 20080269366, whichis herein incorporated by reference for purposes of US patent practice.

In particular, such films may be useful in membrane filters. Thesefilters are generally thin, polymeric films having a large number ofmicroscopic pores. Membrane filters may be used in filtering suspendedmatter out of liquids or gases or for quantitative separation. Examplesof different types of membrane filters include gas separation membranes,dialysis/hemodialysis membranes, reverse osmosis membranes,ultrafiltration membranes, and microporous membranes. Areas in whichthese types of membranes may be applicable include analyticalapplications, beverages, chemicals, electronics, environmentalapplications, and pharmaceuticals.

In addition, microporous polymeric films may be used as batteryseparators because of their ease of manufacture, chemical inertness andthermal properties. The principal role of a separator is to allow ionsto pass between the electrodes but prevent the electrodes fromcontacting. Hence, the films must be strong to prevent puncture. Also,in lithium-ion batteries the films should shut-down (stop ionicconduction) at certain temperatures to prevent thermal runaway of thebattery. Ideally, the resins used for the separator should have highstrength over a large temperature window to allow for either thinnerseparators or more porous separators. Also, for lithium ion batterieslower shut-down temperatures are desired however the film must maintainmechanical integrity after shut-down. Additionally, it is desirable thatthe film maintain dimensional stability at elevated temperatures

The microporous films of the present invention may be used in any of theprocesses or applications as described in, but not limited to, thefollowing patents and patent publications, all of which are hereinincorporated by reference for purposes of US patent practice:WO2005/001956A2; WO2003/100954A2; U.S. Pat. No. 6,586,138; U.S. Pat. No.6,524,742; US 2006/0188786; US 2006/0177643; U.S. Pat. No. 6,749,961;U.S. Pat. No. 6,372,379 and WO 2000/34384A1.

The mesophase separated structure provided by the inventive copolymersprovide several improvements over the prior art for forming microporouspolymeric films. The ordered morphologies result in a greater degree ofcontrol over the pore size and channel structure. The phase separatedmelt morphology also limits film shrinkage in the melt and thereforeimparts a greater dimensional melt stability than in non-phase separatedmaterials.

Photonic Paper, Organic Sensors, Polymerized Composites, Etc.

Interactions of the inventive materials with certain small moleculesresults in swelling of one or both of the domains. This swellingproduces visible color changes that can be useful in applications suchas chemical sensors.

With molecules having low vapor pressures, the swelling is reversibleupon evaporation. This feature can be used to create films that act asphotonic paper, enabling a reusable paper or recording media requiringno pigment for color display as described for a colloidal photonicsystem in Advanced Materials 2003, 15, 892-896

In other cases, the swelling can be accomplished with a material thatcan be fixed after swelling to make a stable composite material.Suitable swelling agents can include polymerizable monomers to createpolymer composites (for an example of colloidal composite systems, see:Advanced Materials 2005, 17, 179-184) or metal precursors to createhybrid organic/inorganic materials

In some embodiments of the invention, the amorphous nature of the softdomains makes them generally more amenable to swelling than thesemicrystalline hard domains. This selective swelling provides a meansfor selective chemical modification of the soft domains, which canimpart differentiated properties.

Distributed Feedback Lasers

The inventive polymers can also be used as a component in a distributedfeedback laser. A distributed feedback laser is a type of laser diode,quantum cascade laser or optical fiber laser where the active region ofthe device is structured as a diffraction grating. The grating, known asa distributed Bragg reflector, provides optical feedback for the laserduring distributed Bragg scattering from the structure. The inventivepolymers could serve as the distributed Bragg reflector. The inventivematerials can also be incorporated into a dynamically tunable thin filmlaser as described in WO2008054363, which is herein incorporated byreference for purposes of US patent practice.

The inventive block interpolymers can also be used to form films withimproved barrier properties. Such materials can be used to form, forexample, bladders in athletic shoes. These materials have particularadvantages for barrier films, in which the barrier is improved becausethe layers physically increase the time to equilibrium saturation ofpenetrants. Some embodiments including semi-crystalline domains orlayers with long range order may show decreases in the permeability ofsmall molecules such as oxygen and water relative to similar polymericmaterials. Such properties may make these inventive copolymers valuablein protective packaging of food and other moisture and air sensitivematerials. The inventive block interpolymers can also display increasedflex crack resistance compared to multilayer films.

The preceding description of the present invention is not intended to belimited to films and may also be present in other articles or objects.

Fibers that may be prepared from the inventive polymers or blendsinclude, but are not limited to, staple fibers, tow, multicomponent,sheath/core, twisted, and monofilament. Suitable fiber forming processesinclude spinbonded, melt blown techniques, as disclosed in U.S. Pat.Nos. 4,430,563, 4,663,220, 4,668,566, and 4,322,027, gel spun fibers asdisclosed in U.S. Pat. No. 4,413,110, woven and nonwoven fabrics, asdisclosed in U.S. Pat. No. 3,485,706, or structures made from suchfibers, including blends with other fibers, such as polyester, nylon orcotton, thermoformed articles, extruded shapes, including profileextrusions and co-extrusions, calendared articles, and drawn, twisted,or crimped yarns or fibers. The new polymers described herein are alsouseful for wire and cable coating operations, as well as in sheetextrusion for vacuum forming operations, and forming molded articles,including the use of injection molding, blow molding process, orrotomolding processes. Compositions comprising the olefin polymers canalso be formed into fabricated articles such as those previouslymentioned using conventional polyolefin processing techniques which arewell known to those skilled in the art of polyolefin processing. Fibersmade from the copolymers may also exhibit optical properties attractivein fabrics and textiles, such as reflective or color-changingcharacteristics.

Dispersions, both aqueous and non-aqueous, can also be formed using theinventive polymers or formulations comprising the same. Frothed foamscomprising the invented polymers can also be formed, as disclosed in PCTapplication No. PCT/US2004/027593, filed Aug. 25, 2004, and published asWO2005/021622. The polymers may also be crosslinked by any known means,such as the use of peroxide, electron beam, silane, azide, or othercross-linking technique. The polymers can also be chemically modified,such as by grafting (for example by use of maleic anhydride (MAH),silanes, or other grafting agent), halogenation, amination, sulfonation,or other chemical modification.

Additives and adjuvants may be included in any formulation comprisingthe inventive polymers. Suitable additives include fillers, such asorganic or inorganic particles, including clays, talc, titanium dioxide,zeolites, powdered metals, organic or inorganic fibers, including carbonfibers, silicon nitride fibers, steel wire or mesh, and nylon orpolyester cording, nano-sized particles, clays, and so forth;tackifiers, oil extenders, including paraffinic or napthelenic oils; andother natural and synthetic polymers, including other polymers accordingto embodiments of the invention.

Suitable polymers for blending with the polymers according toembodiments of the invention include thermoplastic and non-thermoplasticpolymers including natural and synthetic polymers. Exemplary polymersfor blending include polypropylene, (both impact modifyingpolypropylene, isotactic polypropylene, atactic polypropylene, andrandom ethylene/propylene copolymers), various types of polyethylene,including high pressure, free-radical LDPE, Ziegler Natta LLDPE,metallocene PE, including multiple reactor PE (“in reactor” blends ofZiegler-Natta PE and metallocene PE, such as products disclosed in U.S.Pat. Nos. 6,545,088, 6,538,070, 6,566,446, 5,844,045, 5,869,575, and6,448,341), ethylene-vinyl acetate (EVA), ethylene/vinyl alcoholcopolymers, polystyrene, impact modified polystyrene, acrylonitrilebutadiene styrene (ABS), styrene/butadiene block copolymers andhydrogenated derivatives thereof (SBS and SEBS), polyisobutylene (PIB)homopolymer, PIB-isoprene copolymer, EPDM and thermoplasticpolyurethanes. Homogeneous polymers such as olefin plastomers andelastomers, ethylene and propylene-based copolymers (for examplepolymers available under the trade designation VERSIFY™ available fromThe Dow Chemical Company and VISTAMAXX™ available from ExxonMobilChemical Company) can also be useful as components in blends comprisingthe inventive polymers.

Additional end uses include elastic films and fibers; soft touch goods,such as tooth brush handles and appliance handles; gaskets and profiles;adhesives (including hot melt adhesives and pressure sensitiveadhesives); footwear (including shoe soles and shoe liners); autointerior parts and profiles; foam goods (both open and closed cell);impact modifiers for other thermoplastic polymers such as high densitypolyethylene, isotactic polypropylene, or other olefin polymers; coatedfabrics; hoses; tubing; weather stripping; cap liners; flooring; andviscosity index modifiers, also known as pour point modifiers, forlubricants.

In some embodiments, thermoplastic compositions comprising athermoplastic matrix polymer, especially isotactic polypropylene, and anelastomeric multi-block copolymer of ethylene and a copolymerizablecomonomer according to embodiments of the invention, are uniquelycapable of forming core-shell type particles having hard crystalline orsemi-crystalline blocks in the form of a core surrounded by soft orelastomeric blocks forming a “shell” around the occluded domains of hardpolymer. These particles are formed and dispersed within the matrixpolymer by the forces incurred during melt compounding or blending. Thishighly desirable morphology is believed to result due to the uniquephysical properties of the multi-block copolymers which enablecompatible polymer regions such as the matrix and higher comonomercontent elastomeric regions of the multi-block copolymer toself-assemble in the melt due to thermodynamic forces. Shearing forcesduring compounding are believed to produce separated regions of matrixpolymer encircled by elastomer. Upon solidifying, these regions becomeoccluded elastomer particles encased in the polymer matrix.

Particularly desirable blends are thermoplastic polyolefin blends (TPO),thermoplastic elastomer blends (TPE), thermoplastic vulcanizates (TPV)and styrenic polymer blends. TPE and TPV blends may be prepared bycombining the invented multi-block polymers, including functionalized orunsaturated derivatives thereof with an optional rubber, includingconventional block copolymers, especially an SBS block copolymer, andoptionally a crosslinking or vulcanizing agent. TPO blends are generallyprepared by blending the invented multi-block copolymers with apolyolefin, and optionally a crosslinking or vulcanizing agent. Theforegoing blends may be used in forming a molded object, and optionallycrosslinking the resulting molded article. A similar procedure usingdifferent components has been previously disclosed in U.S. Pat. No.6,797,779.

Suitable conventional block copolymers for this application desirablypossess a Mooney viscosity (ML 1+4 @ 100° C.) in the range from 10 to135, more preferably from 25 to 100, and most preferably from 30 to 80.Suitable polyolefins especially include linear or low densitypolyethylene, polypropylene (including atactic, isotactic, syndiotacticand impact modified versions thereof) and poly(4-methyl-1-pentene).Suitable styrenic polymers include polystyrene, rubber modifiedpolystyrene (HIPS), styrene/acrylonitrile copolymers (SAN), rubbermodified SAN (ABS or AES) and styrene maleic anhydride copolymers.

The blends may be prepared by mixing or kneading the respectivecomponents at a temperature around or above the melt point temperatureof one or both of the components. For most multiblock copolymers, thistemperature may be above 130° C., most generally above 145° C., and mostpreferably above 150° C. Typical polymer mixing or kneading equipmentthat is capable of reaching the desired temperatures and meltplastifying the mixture may be employed. These include mills, kneaders,extruders (both single screw and twin-screw), Banbury mixers, calenders,and the like. The sequence of mixing and method may depend on thedesired final composition. A combination of Banbury batch mixers andcontinuous mixers may also be employed, such as a Banbury mixer followedby a mill mixer followed by an extruder. Typically, a TPE or TPVcomposition will have a higher loading of cross-linkable polymer(typically the conventional block copolymer containing unsaturation)compared to TPO compositions. Generally, for TPE and TPV compositions,the weight ratio of conventional block copolymer to multi-blockcopolymer may be from about 90:10 to 10:90, more preferably from 80:20to 20:80, and most preferably from 75:25 to 25:75. For TPO applications,the weight ratio of multi-block copolymer to polyolefin may be fromabout 49:51 to about 5:95, more preferably from 35:65 to about 10:90.For modified styrenic polymer applications, the weight ratio ofmulti-block copolymer to polyolefin may also be from about 49:51 toabout 5:95, more preferably from 35:65 to about 10:90. The ratios may bechanged by changing the viscosity ratios of the various components.There is considerable literature illustrating techniques for changingthe phase continuity by changing the viscosity ratios of theconstituents of a blend that a person skilled in this art may consult ifnecessary.

Certain compositions of the inventive block copolymers also act asplasticizers. A plasticizer is generally an organic compoundincorporated into a high molecular weight polymer, such as for example athermoplastic, to facilitate processing, increase its workability,flexibility, and/or distensibility of the polymer. Polypropylene, forexample, is an engineering thermoplastic that is generally stiff andeven brittle below room temperature especially for highly stereoregularpolypropylene.

Some embodiments of the invention provide miscible blends withpolypropylene. By blending such interpolymer plasticizers withpolypropylene (isotactic polypropylene, syndiotactic polypropylene andatactic polypropylene), the glass transition temperature, storagemodulus and viscosity of the blended polypropylene are lowered. Bydecreasing the transition temperature, storage modulus and viscosity,the workability, flexibility, and distensibility of polypropyleneimproves. As such, broadened commercial application for these newpolypropylene blends in film, fibers and molded products is apparent.Furthermore, the flexibility of a product design utilizing these novelblends can be further extended by taking advantage of the enhancedcomonomer incorporation and tacticity control possible with metalloceneand other homogeneous catalysts, both of which can reduce isotacticpolypropylene crystallinity prior to blending with the inventive blockinterpolymer.

These plasticized polypropylene thermoplastics may be used in knownapplications for polypropylene compositions. These uses include, but arenot limited to: hot melt adhesives; pressure sensitive adhesives (as anadhesive component, particularly when the polypropylene has low levelsof crystallinity, e.g., amorphous polypropylene); films (whetherextrusion coatings, cast or blown; such will exhibit improved heatsealing characteristics); sheets (such as by extrusion in single ormultilayer sheets where at least one layer is a plasticizedpolypropylene thermoplastic composition of the invention); meltblown orspunbond fibers; and, as thermoplastic components in thermoformablethermoplastic olefin (“TPO”) and thermoplastic elastomer (“TPE”) blendswhere polypropylene has traditionally been demonstrated to be effective.In view of these many uses, with improved low temperature properties andincreased workability, the plasticized polypropylene thermoplasticsoffer a suitable replacement in selected applications for plasticizedpolyvinyl chloride (PVC).

The blend compositions may contain processing oils, plasticizers, andprocessing aids. Rubber processing oils and paraffinic, napthenic oraromatic process oils are all suitable for use. Generally from about 0to about 150 parts, more preferably about 0 to about 100 parts, and mostpreferably from about 0 to about 50 parts of oil per 100 parts of totalpolymer are employed. Higher amounts of oil may tend to improve theprocessing of the resulting product at the expense of some physicalproperties. Additional processing aids include conventional waxes, fattyacid salts, such as calcium stearate or zinc stearate, (poly)alcoholsincluding glycols, (poly)alcohol ethers, including glycol ethers,(poly)esters, including (poly)glycol esters, and metal salt-, especiallyGroup 1 or 2 metal or zinc-, salt derivatives thereof.

It is known that non-hydrogenated rubbers such as those comprisingpolymerized forms of butadiene or isoprene, including block copolymers(here-in-after diene rubbers), have lower resistance to UV radiation,ozone, and oxidation, compared to mostly or highly saturated rubbers. Inapplications such as tires made from compositions containing higherconcentrations of diene based rubbers, it is known to incorporate carbonblack to improve rubber stability, along with anti-ozone additives andanti-oxidants. Multi-block copolymers according to the present inventionpossessing extremely low levels of unsaturation, find particularapplication as a protective surface layer (coated, coextruded orlaminated) or weather resistant film adhered to articles formed fromconventional diene elastomer modified polymeric compositions.

For conventional TPO, TPV, and TPE applications, carbon black is theadditive of choice for UV absorption and stabilizing properties.Representative examples of carbon blacks include ASTM N110, N121, N220,N231, N234, N242, N293, N299, S315, N326, N330, M332, N339, N343, N347,N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762,N765, N774, N787, N907, N908, N990 and N991. These carbon blacks haveiodine absorptions ranging from 9 to 145 g/kg and average pore volumesranging from 10 to 150 cm³/100 g. Generally, smaller particle sizedcarbon blacks are employed, to the extent cost considerations permit.For many such applications the present multi-block copolymers and blendsthereof require little or no carbon black, thereby allowing considerabledesign freedom to include alternative pigments or no pigments at all.Multi-hued tires or tires matching the color of the vehicle are onepossibility.

Compositions, including thermoplastic blends according to embodiments ofthe invention may also contain anti-ozonants or anti-oxidants that areknown to a rubber chemist of ordinary skill. The anti-ozonants may bephysical protectants such as waxy materials that come to the surface andprotect the part from oxygen or ozone or they may be chemical protectorsthat react with oxygen or ozone. Suitable chemical protectors includestyrenated phenols, butylated octylated phenol, butylateddi(dimethylbenzyl)phenol, p-phenylenediamines, butylated reactionproducts of p-cresol and dicyclopentadiene (DCPD), polyphenolicantioxidants, hydroquinone derivatives, quinoline, diphenyleneantioxidants, thioester antioxidants, and blends thereof. Somerepresentative trade names of such products are Wingstay™ S antioxidant,Polystay™ 100 antioxidant, Polystay™ 100 AZ antioxidant, Polystay™ 200antioxidant, Wingstay™ L antioxidant, Wingstay™ LHLS antioxidant,Wingstay™ K antioxidant, Wingstay™ 29 antioxidant, Wingstay™ SN-1antioxidant, and Irganox™ antioxidants. In some applications, theanti-oxidants and anti-ozonants used will preferably be non-staining andnon-migratory.

For providing additional stability against UV radiation, hindered aminelight stabilizers (HALS) and UV absorbers may be also used. Suitableexamples include Tinuvin™ 123, Tinuvin™ 144, Tinuvin™ 622, Tinuvin™ 765,Tinuvin™ 770, and Tinuvin™ 780, available from Ciba Specialty Chemicals,and Chemisorb™ T944, available from Cytex Plastics, Houston Tex., USA. ALewis acid may be additionally included with a HALS compound in order toachieve superior surface quality, as disclosed in U.S. Pat. No.6,051,681.

For some compositions, additional mixing processes may be employed topre-disperse the anti-oxidants, anti-ozonants, carbon black, UVabsorbers, and/or light stabilizers to form a masterbatch, andsubsequently to form polymer blends there from.

Suitable crosslinking agents (also referred to as curing or vulcanizingagents) for use herein include sulfur based, peroxide based, or phenolicbased compounds. Examples of the foregoing materials are found in theart, including in U.S. Pat. Nos. 3,758,643; 3,806,558; 5,051,478;4,104,210; 4,130,535; 4,202,801; 4,271,049; 4,340,684; 4,250,273;4,927,882; 4,311,628 and 5,248,729.

When sulfur based curing agents are employed, accelerators and cureactivators may be used as well. Accelerators are used to control thetime and/or temperature required for dynamic vulcanization and toimprove the properties of the resulting cross-linked article. In oneembodiment, a single accelerator or primary accelerator is used. Theprimary accelerator(s) may be used in total amounts ranging from about0.5 to about 4, preferably about 0.8 to about 1.5, phr, based on totalcomposition weight. In another embodiment, combinations of a primary anda secondary accelerator might be used with the secondary acceleratorbeing used in smaller amounts, such as from about 0.05 to about 3 phr,in order to activate and to improve the properties of the cured article.Combinations of accelerators generally produce articles havingproperties that are somewhat better than those produced by use of asingle accelerator. In addition, delayed action accelerators may be usedwhich are not affected by normal processing temperatures yet produce asatisfactory cure at ordinary vulcanization temperatures. Vulcanizationretarders might also be used. Suitable types of accelerators that may beused in the present invention are amines, disulfides, guanidines,thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates andxanthates. Preferably, the primary accelerator is a sulfenamide. If asecond accelerator is used, the secondary accelerator is preferably aguanidine, dithiocarbamate or thiuram compound. Certain processing aidsand cure activators such as stearic acid and ZnO may also be used. Whenperoxide based curing agents are used, co-activators or coagents may beused in combination therewith. Suitable coagents includetrimethylolpropane triacrylate (TMPTA), trimethylolpropanetrimethacrylate (TMPTMA), triallyl cyanurate (TAC), triallylisocyanurate (TAIC), among others. Use of peroxide crosslinkers andoptional coagents used for partial or complete dynamic vulcanization areknown in the art and disclosed for example in the publication, “PeroxideVulcanization of Elastomer”, Vol. 74, No 3, July-August 2001.

When the multi-block copolymer containing composition is at leastpartially crosslinked, the degree of crosslinking may be measured bydissolving the composition in a solvent for specified duration, andcalculating the percent gel or unextractable component. The percent gelnormally increases with increasing crosslinking levels. For curedarticles according to embodiments of the invention, the percent gelcontent is desirably in the range from 5 to 100 percent.

The multi-block copolymers according to embodiments of the invention aswell as blends thereof possess improved processability compared to priorart compositions, due, it is believed, to lower melt viscosity. Thus,the composition or blend demonstrates an improved surface appearance,especially when formed into a molded or extruded article. At the sametime, the present compositions and blends thereof uniquely possessimproved melt strength properties, thereby allowing the presentmulti-block copolymers and blends thereof, especially TPO blends, to beusefully employed in foam and thermoforming applications where meltstrength is currently inadequate.

Thermoplastic compositions according to embodiments of the invention mayalso contain organic or inorganic fillers or other additives such asstarch, talc, calcium carbonate, glass fibers, polymeric fibers(including nylon, rayon, cotton, polyester, and polyaramide), metalfibers, flakes or particles, expandable layered silicates, phosphates orcarbonates, such as clays, mica, silica, alumina, aluminosilicates oraluminophosphates, carbon whiskers, carbon fibers, nanoparticlesincluding nanotubes, wollastonite, graphite, zeolites, and ceramics,such as silicon carbide, silicon nitride or titania. Silane based orother coupling agents may also be employed for better filler bonding.

The thermoplastic compositions according to embodiments of theinvention, including the foregoing blends, may be processed byconventional molding techniques such as injection molding, extrusionmolding, thermoforming, slush molding, over molding, insert molding,blow molding, and other techniques. Films, including multi-layer films,may be produced by cast or tentering processes, including blown filmprocesses.

In addition to the above, the block ethylene/α-olefin interpolymers alsocan be used in a manner that is described in the following U.S.provisional applications, the disclosures of which and theircontinuations, divisional applications and continuation-in-partapplications are incorporated by reference herein in their entirety:

-   -   1) “Impact-Modification of Thermoplastics with        Ethylene/α-Olefins”, U.S. Ser. No. 60/717,928, filed on Sep. 16,        2005;

2) “Three Dimensional Random Looped Structures Made from Interpolymersof Ethylene/α-Olefins and Uses Thereof”, U.S. Ser. No. 60/718,130, filedon Sep. 16, 2005;

3) “Polymer Blends from Interpolymer of Ethylene/α-Olefin”, U.S. Ser.No. 60/717,825, filed on Sep. 16, 2005;

4) “Viscosity Index Improver for Lubricant Compositions”, U.S. Ser. No.60/718,129, filed on Sep. 16, 2005;

5) “Fibers Made from Copolymers of Ethylene/α-Olefins”, U.S. Ser. No.60/718,197, filed on Sep. 16, 2005;

6) “Fibers Made from Copolymers of Propylene/α-Olefins”, U.S. Ser. No.60/717,863, filed on Sep. 16, 2005;

7) “Adhesive and Marking Compositions Made from Interpolymers ofEthylene/α-Olefins”, U.S. Ser. No. 60/718,000, filed on Sep. 16, 2005;

8) “Compositions of Ethylene/α-Olefin Multi-Block Interpolymers SuitableFor Films”, U.S. Ser. No. 60/718,198, filed on Sep. 16, 2005;

9) “Rheology Modification of Interpolymers of Ethylene/α-Olefins andArticles Made Therefrom”, U.S. Ser. No. 60/718,036, filed on Sep. 16,2005;

10) “Soft Foams Made From Interpolymers of Ethylene/α-Olefins”, U.S.Ser. No. 60/717,893, filed on Sep. 16, 2005;

11) “Low Molecular Weight Ethylene/α-Olefin Interpolymer as BaseLubricant Oil”, U.S. Ser. No. 60/717,875, filed on Sep. 16, 2005;

12) “Foams Made From Interpolymers of Ethylene/α-Olefins”, U.S. Ser. No.60/717,860, filed on Sep. 16, 2005;

13) “Compositions of Ethylene/α-Olefin Multi-Block Interpolymer ForBlown Films with High Hot Tack”, U.S. Ser. No. 60/717,982, filed on Sep.16, 2005;

14) “Cap Liners, Closures and Gaskets From Multi-Block Polymers”, U.S.Ser. No. 60/717,824, filed on Sep. 16, 2005;

15) “Polymer Blends From Interpolymers of Ethylene/α-Olefins”, U.S. Ser.No. 60/718,245, filed on Sep. 16, 2005;

16) “Anti-Blocking Compositions Comprising Interpolymers ofEthylene/α-Olefins”, U.S. Ser. No. 60/717,588, filed on Sep. 16, 2005;

17) “Interpolymers of Ethylene/α-Olefins Blends and Profiles and GasketsMade Therefrom”, U.S. Ser. No. 60/718,165, filed on Sep. 16, 2005;

18) “Filled Polymer Compositions Made from Interpolymers ofEthylene/α-Olefins and Uses Thereof”, U.S. Ser. No. 60/717,587, filed onSep. 16, 2005;

19) “Compositions Of Ethylene/α-Olefin Multi-Block Interpolymer ForElastic Films and Laminates”, U.S. Ser. No. 60/718,081, filed on Sep.16, 2005;

20) “Thermoplastic Vulcanizate Comprising Interpolymers ofEthylene/α-Olefins”, U.S. Ser. No. 60/718,186, filed on Sep. 16, 2005;

21) “Multi-Layer, Elastic Articles”, U.S. Ser. No. 60/754,087, filed onDec. 27, 2005; and

22) “Functionalized Olefin Interpolymers, Compositions and ArticlesPrepared Therefrom, and Methods for Making the Same”, U.S. Ser. No.60/718,184, filed on Sep. 16, 2005.

EXAMPLES

The following examples are provided to illustrate the synthesis of theinventive polymers. Certain comparisons are made with some existingpolymers. The examples are presented to exemplify embodiments of theinvention but are not intended to limit the invention to the specificembodiments set forth. Unless indicated to the contrary, all parts andpercentages are by weight. All numerical values are approximate. Whennumerical ranges are given, it should be understood that embodimentsoutside the stated ranges may still fall within the scope of theinvention. Specific details described in each example should not beconstrued as necessary features of the invention.

Testing Methods

In the examples that follow, the following analytical techniques areemployed:

GPC Method for Samples 1-4 and A-C

An automated liquid-handling robot equipped with a heated needle set to160° C. is used to add enough 1,2,4-trichlorobenzene stabilized with 300ppm Ionol to each dried polymer sample to give a final concentration of30 mg/mL. A small glass stir rod is placed into each tube and thesamples are heated to 160° C. for 2 hours on a heated, orbital-shakerrotating at 250 rpm. The concentrated polymer solution is then dilutedto 1 mg/ml using the automated liquid-handling robot and the heatedneedle set to 160° C.

A Symyx Rapid GPC system is used to determine the molecular weight datafor each sample. A Gilson 350 pump set at 2.0 ml/min flow rate is usedto pump helium-purged 1,2-dichlorobenzene stabilized with 300 ppm Ionolas the mobile phase through three Plgel 10 micrometer (μm) Mixed B 300mm×7.5 mm columns placed in series and heated to 160° C. A Polymer LabsELS 1000 Detector is used with the Evaporator set to 250° C., theNebulizer set to 165° C., and the nitrogen flow rate set to 1.8 SLM at apressure of 60-80 psi (400−600 kPa) N₂. The polymer samples are heatedto 160° C. and each sample injected into a 250 n1 loop using theliquid-handling robot and a heated needle. Serial analysis of thepolymer samples using two switched loops and overlapping injections areused. The sample data is collected and analyzed using Symyx Epoch™software. Peaks are manually integrated and the molecular weightinformation reported uncorrected against a polystyrene standardcalibration curve.

Standard CRYSTAF Method

Branching distributions are determined by crystallization analysisfractionation (CRYSTAF) using a CRYSTAF 200 unit commercially availablefrom PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,4trichlorobenzene at 160° C. (0.66 mg/mL) for 1 hr and stabilized at 95°C. for 45 minutes. The sampling temperatures range from 95 to 30° C. ata cooling rate of 0.2° C./min. An infrared detector is used to measurethe polymer solution concentrations. The cumulative solubleconcentration is measured as the polymer crystallizes while thetemperature is decreased. The analytical derivative of the cumulativeprofile reflects the short chain branching distribution of the polymer.

The CRYSTAF peak temperature and area are identified by the peakanalysis module included in the CRYSTAF Software (Version 2001.b,PolymerChar, Valencia, Spain). The CRYSTAF peak finding routineidentifies a peak temperature as a maximum in the dW/dT curve and thearea between the largest positive inflections on either side of theidentified peak in the derivative curve. To calculate the CRYSTAF curve,the preferred processing parameters are with a temperature limit of 70°C. and with smoothing parameters above the temperature limit of 0.1, andbelow the temperature limit of 0.3.

DSC Standard Method (Excluding Samples 1-4 and A-C)

Differential Scanning Calorimetry results are determined using a TAImodel Q1000 DSC equipped with an RCS cooling accessory and anautosampler. A nitrogen purge gas flow of 50 ml/min is used. The sampleis pressed into a thin film and melted in the press at about 175° C. andthen air-cooled to room temperature (25° C.). 3-10 mg of material isthen cut into a 6 mm diameter disk, accurately weighed, placed in alight aluminum pan (ca 50 mg), and then crimped shut. The thermalbehavior of the sample is investigated with the following temperatureprofile. The sample is rapidly heated to 180° C. and held isothermal for3 minutes in order to remove any previous thermal history. The sample isthen cooled to −40° C. at 10° C./min cooling rate and held at −40° C.for 3 minutes. The sample is then heated to 150° C. at 10° C./minheating rate. The cooling and second heating curves are recorded.

The DSC melting peak is measured as the maximum in heat flow rate (W/g)with respect to the linear baseline drawn between −30° C. and end ofmelting. The heat of fusion is measured as the area under the meltingcurve between −30° C. and the end of melting using a linear baseline.

Calibration of the DSC is done as follows. First, a baseline is obtainedby running a DSC from −90° C. without any sample in the aluminum DSCpan. Then 7 milligrams of a fresh indium sample is analyzed by heatingthe sample to 180° C., cooling the sample to 140° C. at a cooling rateof 10° C./min followed by keeping the sample isothermally at 140° C. for1 minute, followed by heating the sample from 140° C. to 180° C. at aheating rate of 10° C. per minute. The heat of fusion and the onset ofmelting of the indium sample are determined and checked to be within0.5° C. from 156.6° C. for the onset of melting and within 0.5 J/g from28.71 J/g for the of fusion. Then deionized water is analyzed by coolinga small drop of fresh sample in the DSC pan from 25° C. to −30° C. at acooling rate of 10° C. per minute. The sample is kept isothermally at−30° C. for 2 minutes and heat to 30° C. at a heating rate of 10° C. perminute. The onset of melting is determined and checked to be within 0.5°C. from 0° C.

GPC Method (Excluding Samples 1-4 and A-C)

The gel permeation chromatographic system consists of either a PolymerLaboratories Model PL-210 or a Polymer Laboratories Model PL-220instrument. The column and carousel compartments are operated at 140° C.Three Polymer Laboratories 10-micron Mixed-B columns are used. Thesolvent is 1,2,4 trichlorobenzene. The samples are prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solventcontaining 200 ppm of butylated hydroxytoluene (BHT). Samples areprepared by agitating lightly for 2 hours at 160° C. The injectionvolume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least adecade of separation between individual molecular weights. The standardsare purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards are prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000, and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards are dissolved at 80° C. with gentleagitation for 30 minutes. The narrow standards mixtures are run firstand in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightsare converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. Sci., Polym.Let., 6, 621 (1968)): M_(polyethylene)=0.431(M_(polystyrene)).

Polyethylene equivalent molecular weight calculations are performedusing Viscotek TriSEC software Version 3.0.

Compression Set

Compression set is measured according to ASTM D 395. The sample isprepared by stacking 25.4 mm diameter round discs of 3.2 mm, 2.0 mm, and0.25 mm thickness until a total thickness of 12.7 mm is reached. Thediscs are cut from 12.7 cm×12.7 cm compression molded plaques moldedwith a hot press under the following conditions: zero pressure for 3 minat 190° C., followed by 86 MPa for 2 min at 190° C., followed by coolinginside the press with cold running water at 86 MPa.

Density

Samples for density measurement are prepared according to ASTM D 1928.Measurements are made within one hour of sample pressing using ASTMD792, Method B.

Flexural/Secant Modulus/Storage Modulus

Samples are compression molded using ASTM D 1928. Flexural and 2 percentsecant moduli are measured according to ASTM D-790. Storage modulus ismeasured according to ASTM D 5026-01 or equivalent technique.

Optical Properties

Films of 0.4 mm thickness are compression molded using a hot press(Carver Model #4095-4PR1001R). The pellets are placed betweenpolytetrafluoroethylene sheets, heated at 190° C. at 55 psi (380 kPa)for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min.The film is then cooled in the press with running cold water at 1.3 MPafor 1 min. The compression molded films are used for opticalmeasurements, tensile behavior, recovery, and stress relaxation.

Clarity is measured using BYK Gardner Haze-gard as specified in ASTM D1746.

45° gloss is measured using BYK Gardner Glossmeter Microgloss 45° asspecified in ASTM D-2457

Internal haze is measured using BYK Gardner Haze-gard based on ASTM D1003 Procedure A. Mineral oil is applied to the film surface to removesurface scratches.

Mechanical Properties—Tensile, Hysteresis, and Tear

Stress-strain behavior in uniaxial tension is measured using ASTM D 1708microtensile specimens. Samples are stretched with an Instron at 500%min⁻¹ at 21° C. Tensile strength and elongation at break are reportedfrom an average of 5 specimens.

100% and 300% Hysteresis is determined from cyclic loading to 100% and300% strains using ASTM D 1708 microtensile specimens with an Instron™instrument. The sample is loaded and unloaded at 267% min⁻¹ for 3 cyclesat 21° C. Cyclic experiments at 300% and 80° C. are conducted using anenvironmental chamber. In the 80° C. experiment, the sample is allowedto equilibrate for 45 minutes at the test temperature before testing. Inthe 21° C., 300% strain cyclic experiment, the retractive stress at 150%strain from the first unloading cycle is recorded. Percent recovery forall experiments are calculated from the first unloading cycle using thestrain at which the load returned to the base line. The percent recoveryis defined as:

${\% \mspace{14mu} {Recovery}} = {\frac{ɛ_{f} - ɛ_{s}}{ɛ_{f}} \times 100}$

where ∈_(f) is the strain taken for cyclic loading and ∈_(s) is thestrain where the load returns to the baseline during the 1^(st)unloading cycle.

Stress relaxation is measured at 50 percent strain and 37° C. for 12hours using an Instron™ instrument equipped with an environmentalchamber. The gauge geometry was 76 mm×25 mm×0.4 mm. After equilibratingat 37° C. for 45 min in the environmental chamber, the sample wasstretched to 50% strain at 333% min⁻¹. Stress was recorded as a functionof time for 12 hours. The percent stress relaxation after 12 hours wascalculated using the formula:

${\% \mspace{14mu} {Stress}\mspace{14mu} {Relaxation}} = {\frac{L_{0} - L_{12}}{L_{0}} \times 100}$

where L₀ is the load at 50% strain at 0 time and L₁₂ is the load at 50percent strain after 12 hours.

Tensile notched tear experiments are carried out on samples having adensity of 0.88 g/cc or less using an Instron™ instrument. The geometryconsists of a gauge section of 76 mm×13 mm×0.4 mm with a 2 mm notch cutinto the sample at half the specimen length. The sample is stretched at508 mm min⁻¹ at 21° C. until it breaks. The tear energy is calculated asthe area under the stress-elongation curve up to strain at maximum load.An average of at least 3 specimens are reported.

TMA

Thermal Mechanical Analysis (Penetration Temperature) is conducted on 30mm diameter×3.3 mm thick, compression molded discs, formed at 180° C.and 10 MPa molding pressure for 5 minutes and then air quenched. Theinstrument used is a TMA 7, brand available from Perkin-Elmer. In thetest, a probe with 1.5 mm radius tip (P/N N519-0416) is applied to thesurface of the sample disc with 1N force. The temperature is raised at5° C./min from 25° C. The probe penetration distance is measured as afunction of temperature. The experiment ends when the probe haspenetrated 1 mm into the sample.

DMA

Dynamic Mechanical Analysis (DMA) is measured on compression moldeddisks formed in a hot press at 180° C. at 10 MPa pressure for 5 minutesand then water cooled in the press at 90° C./min. Testing is conductedusing an ARES controlled strain rheometer (TA instruments) equipped withdual cantilever fixtures for torsion testing.

A 1.5 mm plaque is pressed and cut in a bar of dimensions 32×12 mm. Thesample is clamped at both ends between fixtures separated by 10 mm (gripseparation ΔL) and subjected to successive temperature steps from −100°C. to 200° C. (5° C. per step). At each temperature the torsion modulusG′ is measured at an angular frequency of 10 rad/s, the strain amplitudebeing maintained between 0.1 percent and 4 percent to ensure that thetorque is sufficient and that the measurement remains in the linearregime.

An initial static force of 10 g is maintained (auto-tension mode) toprevent slack in the sample when thermal expansion occurs. As aconsequence, the grip separation ΔL increases with the temperature,particularly above the melting or softening point of the polymer sample.The test stops at the maximum temperature or when the gap between thefixtures reaches 65 mm

Pellet Blocking Strength

Pellet blocking strength can be measured as follows: pellets (150 g) areloaded into a 2″ (5 cm) diameter hollow cylinder that is made of twohalves held together by a hose clamp. A 2.75 lb (1.25 kg) load isapplied to the pellets in the cylinder at 45° C. for 3 days. After 3days, the pellets loosely consolidate into a cylindrical shaped plug.The plug is removed from the form and the pellet blocking force measuredby loading the cylinder of blocked pellets in compression using anInstron™ instrument to measure the compressive force needed to break thecylinder into pellets.

Melt Index

Melt index, or I₂, is measured in accordance with ASTM D 1238, Condition190° C./2.16 kg. Melt index, or I₁₀ is also measured in accordance withASTM D 1238, Condition 190° C./10 kg.

ATREF

Analytical temperature rising elution fractionation (ATREF) analysis isconducted according to the method described in U.S. Pat. No. 4,798,081and Wilde, L.; Ryle, T. R.; Knobeloch, D. C.; Peat, I. R.; Determinationof Branching Distributions in Polyethylene and Ethylene Copolymers, J.Polym. Sci., 20, 441-455 (1982), which are incorporated by referenceherein in their entirety. The composition to be analyzed is dissolved intrichlorobenzene and allowed to crystallize in a column containing aninert support (stainless steel shot) by slowly reducing the temperatureto 20° C. at a cooling rate of 0.1° C./min. The column is equipped withan infrared detector. An ATREF chromatogram curve is then generated byeluting the crystallized polymer sample from the column by slowlyincreasing the temperature of the eluting solvent (trichlorobenzene)from 20 to 120° C. at a rate of 1.5° C./min.

¹³C NMR Analysis

The samples are prepared by adding approximately 3 g of a 50/50 mixtureof tetrachloroethane-d²/orthodichlorobenzene to 0.4 g sample in a 10 mmNMR tube. The samples are dissolved and homogenized by heating the tubeand its contents to 150° C. The data are collected using a JEOL Eclipse™400 MHz spectrometer or a Varian Unity Plus™ 400 MHz spectrometer,corresponding to a ¹³C resonance frequency of 100.5 MHz. The data areacquired using 4000 transients per data file with a 6 second pulserepetition delay. To achieve minimum signal-to-noise for quantitativeanalysis, multiple data files are added together. The spectral width is25,000 Hz with a minimum file size of 32K data points. The samples areanalyzed at 130° C. in a 10 mm broad band probe. The comonomerincorporation is determined using Randall's triad method (Randall, J.C.; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989), which isincorporated by reference herein in its entirety.

Polymer Fractionation by TREF (also Known as Preparative TREF)

Large-scale TREF fractionation is carried by dissolving 15-20 g ofpolymer in 2 liters of 1,2,4-trichlorobenzene (TCB) by stirring for 4hours at 160° C. The polymer solution is forced by 15 psig (100 kPa)nitrogen onto a 3 inch by 4 foot (7.6 cm×12 cm) steel column packed witha 60:40 (v:v) mix of 30-40 mesh (600-425 nm) spherical, technicalquality glass beads (available from Potters Industries, HC 30 Box 20,Brownwood, Tex., 76801) and stainless steel, 0.028″ (0.7 mm) diametercut wire shot (available from Pellets, Inc. 63 Industrial Drive, NorthTonawanda, N.Y., 14120). The column is immersed in a thermallycontrolled oil jacket, set initially to 160° C. The column is firstcooled ballistically to 125° C., then slow cooled to 20° C. at 0.04° C.per minute and held for one hour. Fresh TCB is introduced at about 65ml/min while the temperature is increased at 0.167° C. per minute.

Approximately 2000 ml portions of eluant from the preparative TREFcolumn are collected in a 16 station, heated fraction collector. Thepolymer is concentrated in each fraction using a rotary evaporator untilabout 50 to 100 ml of the polymer solution remains. The concentratedsolutions are allowed to stand overnight before adding excess methanol,filtering, and rinsing (approx. 300-500 ml of methanol including thefinal rinse). The filtration step is performed on a 3 position vacuumassisted filtering station using 5.0 nm polytetrafluoroethylene coatedfilter paper (available from Osmonics Inc., Cat#Z50WP04750). Thefiltrated fractions are dried overnight in a vacuum oven at 60° C. andweighed on an analytical balance before further testing. Additionalinformation about hits method is taught in Wilde, L.; Ryle, T. R.;Knobeloch, D. C.; Peat, I. R.; Determination of Branching Distributionsin Polyethylene and Ethylene Copolymers, J. Polym. Sci., 20, 441-455(1982),

Melt Strength

Melt Strength (MS) is measured by using a capillary rheometer fittedwith a 2.1 mm diameter, 20:1 die with an entrance angle of approximately45 degrees. After equilibrating the samples at 190° C. for 10 minutes,the piston is run at a speed of 1 inch/minute (2.54 cm/minute). Thestandard test temperature is 190° C. The sample is drawn uniaxially to aset of accelerating nips located 100 mm below the die with anacceleration of 2.4 mm/sec². The required tensile force is recorded as afunction of the take-up speed of the nip rolls. The maximum tensileforce attained during the test is defined as the melt strength. In thecase of polymer melt exhibiting draw resonance, the tensile force beforethe onset of draw resonance was taken as melt strength. The meltstrength is recorded in centiNewtons (“cN”).

Catalysts

The term “overnight”, if used, refers to a time of approximately 16-18hours, the term “room temperature”, refers to a temperature of 20-25°C., and the term “mixed alkanes” refers to a commercially obtainedmixture of C₆₋₉ aliphatic hydrocarbons available under the tradedesignation Isopar E®, from ExxonMobil Chemical Company. In the eventthe name of a compound herein does not conform to the structuralrepresentation thereof, the structural representation shall control. Thesynthesis of all metal complexes and the preparation of all screeningexperiments were carried out in a dry nitrogen atmosphere using dry boxtechniques. All solvents used were HPLC grade and were dried beforetheir use.

MMAO refers to modified methylalumoxane, a triisobutylaluminum modifiedmethylalumoxane available commercially from Akzo-Noble Corporation.

The preparation of catalyst (B1) is conducted as follows.

a) Preparation of(1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)methylimine

3,5-Di-t-butylsalicylaldehyde (3.00 g) is added to 10 mL ofisopropylamine. The solution rapidly turns bright yellow. After stirringat ambient temperature for 3 hours, volatiles are removed under vacuumto yield a bright yellow, crystalline solid (97 percent yield).

b) Preparation of1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconium dibenzyl

A solution of (1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)imine (605mg, 2.2 mmol) in 5 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (500 mg, 1.1 mmol) in 50 mL toluene. The resulting darkyellow solution is stirred for 30 min Solvent is removed under reducedpressure to yield the desired product as a reddish-brown solid.

The preparation of catalyst (B2) is conducted as follows.

a) Preparation of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine

2-Methylcyclohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol(90 mL), and di-t-butylsalicaldehyde (10.00 g, 42.67 mmol) is added. Thereaction mixture is stirred for three hours and then cooled to −25° C.for 12 hrs. The resulting yellow solid precipitate is collected byfiltration and washed with cold methanol (2×15 mL), and then dried underreduced pressure. The yield is 11.17 g of a yellow solid. ¹H NMR isconsistent with the desired product as a mixture of isomers.

b) Preparation ofbis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl

A solution of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine (7.63g, 23.2 mmol) in 200 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (5.28 g, 11.6 mmol) in 600 mL toluene. The resulting darkyellow solution is stirred for 1 hour at 25° C. The solution is dilutedfurther with 680 mL toluene to give a solution having a concentration of0.00783 M.

Cocatalyst 1 A mixture of methyldi(C₁₄₋₁₈alkyl)ammonium salts oftetrakis(pentafluorophenyl)borate (here-in-after armeenium borate),prepared by reaction of a long chain trialkylamine (Armeen™ M2HT,available from Akzo-Nobel, Inc.), HCl and Li[B(C₆F₅)₄], substantially asdisclosed in U.S. Pat. No. 5,919,9883, Ex. 2.

Cocatalyst 2 Mixed C₁₄₋₁₈ alkyldimethylammonium salt ofbis(tris(pentafluorophenyl)-alumane)-2-undecylimidazolide, preparedaccording to U.S. Pat. No. 6,395,671, Ex. 16.

Shuttling Agents The shuttling agents employed include diethylzinc (DEZ,SA1), di(i-butyl)zinc (SA2), di(n-hexyl)zinc (SA3), triethylaluminum(TEA, SA4), trioctylaluminum (SA5), triethylgallium (SA6),i-butylaluminum bis(dimethyl(t-butyl)siloxane) (SA7), i-butylaluminumbis(di(trimethylsilyl)amide) (SA8), n-octylaluminumdi(pyridine-2-methoxide) (SA9), bis(n-octadecyl)i-butylaluminum (SA10),i-butylaluminum bis(di(n-pentyl)amide) (SA11), n-octylaluminumbis(2,6-di-t-butylphenoxide) (SA12), n-octylaluminumdi(ethyl(1-naphthyl)amide) (SA13), ethylaluminumbis(t-butyldimethylsiloxide) (SA14), ethylaluminumdi(bis(trimethylsilyl)amide) (SA15), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA16), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA17), n-octylaluminumbis(dimethyl(t-butyl)siloxide (SA18), ethylzinc (2,6-diphenylphenoxide)(SA19), and ethylzinc (t-butoxide) (SA20).

Examples 1-4 Comparative A-C General High Throughput ParallelPolymerization Conditions

Polymerizations are conducted using a high throughput, parallelpolymerization reactor (PPR) available from Symyx Technologies, Inc. andoperated substantially according to U.S. Pat. Nos. 6,248,540, 6,030,917,6,362,309, 6,306,658, and 6,316,663. Ethylene copolymerizations areconducted at 130° C. and 200 psi (1.4 MPa) with ethylene on demand using1.2 equivalents of cocatalyst 1 based on total catalyst used (1.1equivalents when MMAO is present). A series of polymerizations areconducted in a parallel pressure reactor (PPR) contained of 48individual reactor cells in a 6×8 array that are fitted with apre-weighed glass tube. The working volume in each reactor cell is 6000μL. Each cell is temperature and pressure controlled with stirringprovided by individual stirring paddles. The monomer gas and quench gasare plumbed directly into the PPR unit and controlled by automaticvalves. Liquid reagents are robotically added to each reactor cell bysyringes and the reservoir solvent is mixed alkanes. The order ofaddition is mixed alkanes solvent (4 ml), ethylene, 1-octene comonomer(1 ml), cocatalyst 1 or cocatalyst 1/MMAO mixture, shuttling agent, andcatalyst or catalyst mixture. When a mixture of cocatalyst 1 and MMAO ora mixture of two catalysts is used, the reagents are premixed in a smallvial immediately prior to addition to the reactor. When a reagent isomitted in an experiment, the above order of addition is otherwisemaintained. Polymerizations are conducted for approximately 1-2 minutes,until predetermined ethylene consumptions are reached. After quenchingwith CO, the reactors are cooled and the glass tubes are unloaded. Thetubes are transferred to a centrifuge/vacuum drying unit, and dried for12 hours at 60° C. The tubes containing dried polymer are weighed andthe difference between this weight and the tare weight gives the netyield of polymer. Results are contained in Table 1. In Table 1 andelsewhere in the application, comparative compounds are indicated by anasterisk (*).

Examples 1-4 demonstrate the synthesis of linear block copolymers by thepresent invention as evidenced by the formation of a very narrow MWD,essentially monomodal copolymer when DEZ is present and a bimodal, broadmolecular weight distribution product (a mixture of separately producedpolymers) in the absence of DEZ. Due to the fact that Catalyst (A1) isknown to incorporate more octene than Catalyst (B1), the differentblocks or segments of the resulting copolymers according to embodimentsof the invention are distinguishable based on branching or density.

TABLE 1 Cat. (A1) Cat (B1) Cocat MMAO shuttling Ex. (μmol) (μmol) (μmol)(μmol) agent (μmol) Yield (g) Mn Mw/Mn hexyls¹ A* 0.06 — 0.066 0.3 —0.1363 300502 3.32 — B* — 0.1 0.110 0.5 — 0.1581 36957 1.22 2.5 C* 0.060.1 0.176 0.8 — 0.2038 45526 5.30² 5.5 1 0.06 0.1 0.192 — DEZ (8.0) 0.1974 28715 1.19 4.8 2 0.06 0.1 0.192 — DEZ (80.0) 0.1468 2161 1.1214.4  3 0.06 0.1 0.192 — TEA (8.0)  0.208 22675 1.71 4.6 4 0.06 0.10.192 — TEA (80.0) 0.1879 3338 1.54 9.4 ¹C₆ or higher chain content per1000 carbons ²Bimodal molecular weight distribution

It may be seen the polymers produced according to embodiments of theinvention have a relatively narrow polydispersity (Mw/Mn) and largerblock-copolymer content (trimer, tetramer, or larger) than polymersprepared in the absence of the shuttling agent.

Further characterizing data for the polymers of Table 1 are determinedby reference to the figures. More specifically DSC and ATREF resultsshow the following:

The DSC curve for the polymer of Example 1 shows a 115.7° C. meltingpoint (Tm) with a heat of fusion of 158.1 J/g. The corresponding CRYSTAFcurve shows the tallest peak at 34.5° C. with a peak area of 52.9percent. The difference between the DSC Tm and the Tcrystaf is 81.2° C.

The DSC curve for the polymer of Example 2 shows a peak with a 109.7° C.melting point (Tm) with a heat of fusion of 214.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 46.2° C. with a peak area of57.0 percent. The difference between the DSC Tm and the Tcrystaf is63.5° C.

The DSC curve for the polymer of Example 3 shows a peak with a 120.7° C.melting point (Tm) with a heat of fusion of 160.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 66.1° C. with a peak area of71.8 percent. The difference between the DSC Tm and the Tcrystaf is54.6° C.

The DSC curve for the polymer of Example 4 shows a peak with a 104.5° C.melting point (Tm) with a heat of fusion of 170.7 J/g. The correspondingCRYSTAF curve shows the tallest peak at 30° C. with a peak area of 18.2percent. The difference between the DSC Tm and the Tcrystaf is 74.5° C.

The DSC curve for comparative A shows a 90.0° C. melting point (Tm) witha heat of fusion of 86.7 J/g. The corresponding CRYSTAF curve shows thetallest peak at 48.5° C. with a peak area of 29.4 percent. Both of thesevalues are consistent with a resin that is low in density. Thedifference between the DSC Tm and the Tcrystaf is 41.8° C.

The DSC curve for comparative B shows a 129.8° C. melting point (Tm)with a heat of fusion of 237.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 82.4° C. with a peak area of 83.7 percent.Both of these values are consistent with a resin that is high indensity. The difference between the DSC Tm and the Tcrystaf is 47.4° C.

The DSC curve for comparative C shows a 125.3° C. melting point (Tm)with a heat of fusion of 143.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 81.8° C. with a peak area of 34.7 percent aswell as a lower crystalline peak at 52.4° C. The separation between thetwo peaks is consistent with the presence of a high crystalline and alow crystalline polymer. The difference between the DSC Tm and theTcrystaf is 43.5° C.

Examples 5-19 Comparatives D-F, Continuous Solution Polymerization,Catalyst A1/B2+DEZ

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil ChemicalCompany), ethylene at 2.70 lbs/hour (1.22 kg/hour), 1-octene, andhydrogen (where used) are supplied to a 3.8 L reactor equipped with ajacket for temperature control and an internal thermocouple. The solventfeed to the reactor is measured by a mass-flow controller. A variablespeed diaphragm pump controls the solvent flow rate and pressure to thereactor. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst and cocatalyst 1 injection lines and thereactor agitator. These flows are measured by Micro-Motion mass flowmeters and controlled by control valves or by the manual adjustment ofneedle valves. The remaining solvent is combined with 1-octene,ethylene, and hydrogen (where used) and fed to the reactor. A mass flowcontroller is used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters and are combined with the catalystflush solvent and introduced into the bottom of the reactor. The reactoris run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.Product is removed through exit lines at the top of the reactor. Allexit lines from the reactor are steam traced and insulated.Polymerization is stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream is thenheated by passing through a heat exchanger before devolatilization. Thepolymer product is recovered by extrusion using a devolatilizingextruder and water cooled pelletizer. Process details and results arecontained in Table 2. Selected polymer properties are provided in Table3.

TABLE 2 Process details for preparation of ethylene/α-olefin blockcopolymers Cat Cat A1 Cat B2 DEZ DEZ Cocat Cocat Poly C₈H₁₆ Solv. H₂ TA1² Flow B2³ Flow Conc Flow Conc. Flow [C₂H₄]/ Rate⁵ Conv Solids Ex.kg/hr kg/hr sccm¹ ° C. ppm kg/hr ppm kg/hr % kg/hr ppm kg/hr [DEZ]⁴kg/hr %⁶ % Eff.⁷ D* 1.63 12.7 29.90 120 142.2  0.14 — — 0.19 0.32  8200.17 536 1.81 88.8 11.2 95.2 E* ″  9.5 5.00 ″ — — 109   0.10 0.19 ″ 17430.40 485 1.47 89.9 11.3 126.8 F* ″ 11.3 251.6 ″ 71.7 0.06 30.8 0.06 — —″ 0.11 — 1.55 88.5 10.3 257.7  5 ″ ″ — ″ ″ 0.14 30.8 0.13 0.17 0.43 ″0.26 419 1.64 89.6 11.1 118.3  6 ″ ″ 4.92 ″ ″ 0.10 30.4 0.08 0.17 0.32 ″0.18 570 1.65 89.3 11.1 172.7  7 ″ ″ 21.70 ″ ″ 0.07 30.8 0.06 0.17 0.25″ 0.13 718 1.60 89.2 10.6 244.1  8 ″ ″ 36.90 ″ ″ 0.06 ″ ″ ″ 0.10 ″ 0.121778  1.62 90.0 10.8 261.1  9 ″ ″ 78.43 ″ ″ ″ ″ ″ ″ 0.04 ″ ″ 4596  1.6390.2 10.8 267.9 10 ″ ″ 0.00 123 71.1 0.12 30.3 0.14 0.34 0.19 1743 0.08415 1.67 90.31 11.1 131.1 11 ″ ″ ″ 120 71.1 0.16 ″ 0.17 0.80 0.15 17430.10 249 1.68 89.56 11.1 100.6 12 ″ ″ ″ 121 71.1 0.15 ″ 0.07 ″ 0.09 17430.07 396 1.70 90.02 11.3 137.0 13 ″ ″ ″ 122 71.1 0.12 ″ 0.06 ″ 0.05 17430.05 653 1.69 89.64 11.2 161.9 14 ″ ″ ″ 120 71.1 0.05 ″ 0.29 ″ 0.10 17430.10 395 1.41 89.42 9.3 114.1 15 2.45 ″ ″ ″ 71.1 0.14 ″ 0.17 ″ 0.14 17430.09 282 1.80 89.33 11.3 121.3 16 ″ ″ ″ 122 71.1 0.10 ″ 0.13 ″ 0.07 17430.07 485 1.78 90.11 11.2 159.7 17 ″ ″ ″ 121 71.1 0.10 ″ 0.14 ″ 0.08 1743″ 506 1.75 89.08 11.0 155.6 18 0.69 ″ ″ 121 71.1 ″ ″ 0.22 ″ 0.11 17430.10 331 1.25 89.93 8.8 90.2 19 0.32 ″ ″ 122 71.1 0.06 ″ ″ ″ 0.09 17430.08 367 1.16 90.74 8.4 106.0 *Comparative, not an example of theinvention ¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl ⁴molar ratio in reactor ⁵polymer production rate⁶percent ethylene conversion in reactor ⁷efficiency, kg polymer/g Mwhere g M = g Hf + g Zr

TABLE 3 Properties of ethylene/α-olefin block copolymers Heat of Tm −CRYSTAF Density Mw Mn Fusion T_(m) T_(c) T_(CRYSTAF) T_(CRYSTAF) PeakArea Ex. (g/cm³) I₂ I₁₀ I₁₀/I₂ (g/mol) (g/mol) Mw/Mn (J/g) (° C.) (° C.)(° C.) (° C.) (percent) D* 0.8627 1.5 10.0 6.5 110,000 55,800 2.0 32 3745 30 7 99 E* 0.9378 7.0 39.0 5.6 65,000 33,300 2.0 183 124 113 79 45 95F* 0.8895 0.9 12.5 13.4 137,300 9,980 13.8 90 125 111 78 47 20  5 0.87861.5 9.8 6.7 104,600 53,200 2.0 55 120 101 48 72 60  6 0.8785 1.1 7.5 6.5109600 53300 2.1 55 115 94 44 71 63  7 0.8825 1.0 7.2 7.1 118,500 53,1002.2 69 121 103 49 72 29  8 0.8828 0.9 6.8 7.7 129,000 40,100 3.2 68 124106 80 43 13  9 0.8836 1.1 9.7 9.1 129600 28700 4.5 74 125 109 81 44 1610 0.8784 1.2 7.5 6.5 113,100 58,200 1.9 54 116 92 41 75 52 11 0.88189.1 59.2 6.5 66,200 36,500 1.8 63 114 93 40 74 25 12 0.8700 2.1 13.2 6.4101,500 55,100 1.8 40 113 80 30 83 91 13 0.8718 0.7 4.4 6.5 132,10063,600 2.1 42 114 80 30 81 8 14 0.9116 2.6 15.6 6.0 81,900 43,600 1.9123 121 106 73 48 92 15 0.8719 6.0 41.6 6.9 79,900 40,100 2.0 33 114 9132 82 10 16 0.8758 0.5 3.4 7.1 148,500 74,900 2.0 43 117 96 48 69 65 170.8757 1.7 11.3 6.8 107,500 54,000 2.0 43 116 96 43 73 57 18 0.9192 4.124.9 6.1 72,000 37,900 1.9 136 120 106 70 50 94 19 0.9344 3.4 20.3 6.076,800 39,400 1.9 169 125 112 80 45 88

Physical Property Testing

Polymer samples are evaluated for physical properties such as hightemperature resistance properties, as evidenced by TMA temperaturetesting, pellet blocking strength, high temperature recovery, hightemperature compression set and storage modulus ratio, G′(25°C.)/G′(100° C.). Several commercially available polymers are included inthe tests: Comparative G* is a substantially linear ethylene/1-octenecopolymer (AFFINITY®, available from The Dow Chemical Company),Comparative H* is an elastomeric, substantially linear ethylene/1-octenecopolymer (AFFINITY® EG8100, available from The Dow Chemical Company),Comparative I is a substantially linear ethylene/1-octene copolymer(AFFINITY® PL1840, available from The Dow Chemical Company), ComparativeJ is a hydrogenated styrene/butadiene/styrene triblock copolymer(KRATON™ G1652, available from KRATON Polymers), Comparative K is athermoplastic vulcanizate (TPV, a polyolefin blend containing dispersedtherein a crosslinked elastomer). Results are presented in Table 4.

TABLE 4 High Temperature Mechanical Properties Pellet 300% BlockingStrain Compression TMA-1 mm Strength Recovery Set penetration lb/ft²G′(25° C.)/ (80° C.) (70° C.) Ex. (° C.) (kPa) G′(100° C.) (percent)(percent) D* 51 — 9 Failed — E* 130 — 18 — — F* 70 141 (6.8)  9 Failed100   5 104 0 (0)  6 81 49  6 110 — 5 — 52  7 113 — 4 84 43  8 111 — 4Failed 41  9 97 — 4 — 66 10 108 — 5 81 55 11 100 — 8 — 68 12 88 — 8 — 7913 95 — 6 84 71 14 125 — 7 — — 15 96 — 5 — 58 16 113 — 4 — 42 17 108 0(0)  4 82 47 18 125 — 10 — — 19 133 — 9 — — G* 75 463 (22.2) 89 Failed100  H* 70 213 (10.2) 29 Failed 100  I* 111 — 11 — — J* 107 — 5 Failed100  K* 152 — 3 — 40

In Table 4, Comparative F (which is a physical blend of the two polymersresulting from simultaneous polymerizations using catalyst A1 and B1)has a 1 mm penetration temperature of about 70° C., while Examples 5-9have a 1 mm penetration temperature of 100° C. or greater. Further,Examples 10-19 all have a 1 mm penetration temperature of greater than85° C., with most having 1 mm TMA temperature of greater than 90° C. oreven greater than 100° C. This shows that the novel polymers have betterdimensional stability at higher temperatures compared to a physicalblend. Comparative J (a commercial SEBS) has a good 1 mm TMA temperatureof about 107° C., but it has very poor (high temperature 70° C.)compression set of about 100 percent and it also failed to recover(sample broke) during a high temperature (80° C.) 300 percent strainrecovery. Thus the exemplified polymers have a unique combination ofproperties unavailable even in some commercially available, highperformance thermoplastic elastomers.

Similarly, Table 4 shows a low (good) storage modulus ratio, G′(25°C.)/G′(100° C.), for the inventive polymers of 6 or less, whereas aphysical blend (Comparative F) has a storage modulus ratio of 9 and arandom ethylene/octene copolymer (Comparative G) of similar density hasa storage modulus ratio an order of magnitude greater (89). It isdesirable that the storage modulus ratio of a polymer be as close to 1as possible. Such polymers will be relatively unaffected by temperature,and fabricated articles made from such polymers can be usefully employedover a broad temperature range. This feature of low storage modulusratio and temperature independence is particularly useful in elastomerapplications such as in pressure sensitive adhesive formulations.

The data in Table 4 also demonstrate that the polymers according toembodiments of the invention possess improved pellet blocking strength.In particular, Example 5 has a pellet blocking strength of 0 MPa,meaning it is free flowing under the conditions tested, compared toComparatives F and G which show considerable blocking. Blocking strengthis important since bulk shipment of polymers having large blockingstrengths can result in product clumping or sticking together uponstorage or shipping, resulting in poor handling properties.

High temperature (70° C.) compression set for the inventive polymers isgenerally good, meaning generally less than about 80 percent, preferablyless than about 70 percent and especially less than about 60 percent. Incontrast, Comparatives F, G, H and J all have a 70° C. compression setof 100 percent (the maximum possible value, indicating no recovery).Good high temperature compression set (low numerical values) isespecially needed for applications such as gaskets, window profiles,o-rings, and the like.

TABLE 5 Ambient Temperature Mechanical Properties Tensile Abrasion:Notched Flex Tensile Tensile Elongation Tensile Elongation Volume TearModulus Modulus Strength at Break¹ Strength at Break Loss Strength Ex.(MPa) (MPa) (MPa)¹ (%) (MPa) (%) (mm³) (mJ) D* 12 5 — — 10 1074 — — E*895 589 — 31 1029 — — F* 57 46 — — 12 824 93 339  5 30 24 14 951 16 111648 —  6 33 29 — — 14 938 — —  7 44 37 15 846 14 854 39 —  8 41 35 13 78514 810 45 461  9 43 38 — — 12 823 — — 10 23 23 — — 14 902 — — 11 30 26 —— 16 1090 — 976 12 20 17 12 961 13 931 — 1247  13 16 14 — — 13 814 — 69114 212 160 — — 29 857 — — 15 18 14 12 1127  10 1573 — 2074  16 23 20 — —12 968 — — 17 20 18 — — 13 1252 — 1274  18 323 239 — — 30 808 — — 19 706483 — — 36 871 — — G* 15 15 — — 17 1000 — 746 H* 16 15 — — 15 829 — 569I* 210 147 — — 29 697 — — J* — — — — 32 609 — — K* — — — — — — — —Retractive 100% Strain 300% Strain Stress Stress Recovery Recovery at150% Compression Relaxation 21° C. 21° C. Strain Set 21° C. at 50% Ex.(percent) (percent) (kPa) (Percent) Strain² D* 91 83 760 — — E* — — — —— F* 78 65 400 42 —  5 87 74 790 14 33  6 — 75 861 13 —  7 82 73 810 20—  8 82 74 760 22 —  9 — — — 25 — 10 86 75 860 12 — 11 89 66 510 14 3012 91 75 700 17 — 13 91 — — 21 — 14 — — — — — 15 89 83 770 14 — 16 88 831040  13 — 17 13 83 920  4 — 18 — — — — — 19 — — — — — G* 86 53 110 2750 H* 87 60 380 23 — I* — — — — — J* 93 96 1900  25 — K* — — — 30 —¹Tested at 51 cm/minute ²measured at 38° C. for 12 hours

Table 5 shows results for mechanical properties for the new polymers aswell as for various comparison polymers at ambient temperatures. It maybe seen that the inventive polymers have very good abrasion resistancewhen tested according to ISO 4649, generally showing a volume loss ofless than about 90 mm³, preferably less than about 80 mm³, andespecially less than about 50 mm³. In this test, higher numbers indicatehigher volume loss and consequently lower abrasion resistance.

Tear strength as measured by tensile notched tear strength of theinventive polymers is generally 1000 mJ or higher, as shown in Table 5.Tear strength for the inventive polymers can be as high as 3000 mJ, oreven as high as 5000 mJ. Comparative polymers generally have tearstrengths no higher than 750 mJ.

Table 5 also shows that the polymers according to embodiments of theinvention have better retractive stress at 150 percent strain(demonstrated by higher retractive stress values) than some of thecomparative samples. Comparative Examples F, G and H have retractivestress value at 150 percent strain of 400 kPa or less, while theinventive polymers have retractive stress values at 150 percent strainof 500 kPa (Ex. 11) to as high as about 1100 kPa (Ex. 17). Polymershaving higher than 150 percent retractive stress values would be quiteuseful for elastic applications, such as elastic fibers and fabrics,especially nonwoven fabrics. Other applications include diaper, hygiene,and medical garment waistband applications, such as tabs and elasticbands.

Table 5 also shows that stress relaxation (at 50 percent strain) is alsoimproved (less) for the inventive polymers as compared to, for example,Comparative G. Lower stress relaxation means that the polymer retainsits force better in applications such as diapers and other garmentswhere retention of elastic properties over long time periods at bodytemperatures is desired.

Optical Testing

TABLE 6 Polymer Haze, Clarity, and Gloss Ex. Internal Haze (percent)Clarity (percent) 45° Gloss (percent) F* 84 22 49 G* 5 73 56  5 13 72 60 6 33 69 53  7 28 57 59  8 20 65 62  9 61 38 49 10 15 73 67 11 13 69 6712 8 75 72 13 7 74 69 14 59 15 62 15 11 74 66 16 39 70 65 17 29 73 66 1861 22 60 19 74 11 52 G* 5 73 56 H* 12 76 59 I* 20 75 59

The haze, clarity, and gloss values reported in Table 6 are based oncompression molded films substantially lacking in orientation. Opticalproperties of the polymers may be varied over wide ranges, due tovariation in crystallite size, resulting from variation in the quantityof chain shuttling agent employed in the polymerization. In addition,the crystallite size may also be controlled through various processingmethods and quenching conditions as well as through manipulation of thelevel of comonomer and hard segment content.

Extractions of Multi-Block Copolymers

Extraction studies of the polymers of Examples 5, 7 and Comparative Eare conducted. In the experiments, the polymer sample is weighed into aglass fritted extraction thimble and fitted into a Kumagawa typeextractor. The extractor with sample is purged with nitrogen, and a 500mL round bottom flask is charged with 350 mL of diethyl ether. The flaskis then fitted to the extractor. The ether is heated while beingstirred. Time is noted when the ether begins to condense into thethimble, and the extraction is allowed to proceed under nitrogen for 24hours. At this time, heating is stopped and the solution is allowed tocool. Any ether remaining in the extractor is returned to the flask. Theether in the flask is evaporated under vacuum at ambient temperature,and the resulting solids are purged dry with nitrogen. Any residue istransferred to a weighed bottle using successive washes of hexane. Thecombined hexane washes are then evaporated with another nitrogen purge,and the residue dried under vacuum overnight at 40° C. Any remainingether in the extractor is purged dry with nitrogen.

A second clean round bottom flask charged with 350 mL of hexane is thenconnected to the extractor. The hexane is heated to reflux with stirringand maintained at reflux for 24 hours after hexane is first noticedcondensing into the thimble. Heating is then stopped and the flask isallowed to cool. Any hexane remaining in the extractor is transferredback to the flask. The hexane is removed by evaporation under vacuum atambient temperature, and any residue remaining in the flask istransferred to a weighed bottle using successive hexane washes. Thehexane in the flask is evaporated by a nitrogen purge, and the residueis vacuum dried overnight at 40° C.

The polymer sample remaining in the thimble after the extractions istransferred from the thimble to a weighed bottle and vacuum driedovernight at 40° C. Results are contained in Table 7.

TABLE 7 ether ether hexane hexane residue wt. soluble soluble C₈ molesoluble soluble C₈ mole C₈ mole Sample (g) (g) (percent) percent¹ (g)(percent) percent¹ percent¹ Comp. F* 1.097 0.063 5.69 12.2 0.245 22.3513.6 6.5 Ex. 5 1.006 0.041 4.08 — 0.040 3.98 14.2 11.6 Ex. 7 1.092 0.0171.59 13.3 0.012 1.10 11.7 9.9 Determined by ¹³C NMR

Additional Polymer Examples 19A-I, Continuous Solution Polymerization,Catalyst A1/B2+DEZ Examples 19A-I

Continuous solution polymerizations are carried out in a computercontrolled well-mixed reactor. Purified mixed alkanes solvent (Isopar™ Eavailable from Exxon Mobil Chemical Company), ethylene, 1-octene, andhydrogen (where used) are combined and fed to a 27 gallon reactor. Thefeeds to the reactor are measured by mass-flow controllers. Thetemperature of the feed stream is controlled by use of a glycol cooledheat exchanger before entering the reactor. The catalyst componentsolutions are metered using pumps and mass flow meters. The reactor isrun liquid-full at approximately 550 psig pressure. Upon exiting thereactor, water and additive are injected in the polymer solution. Thewater hydrolyzes the catalysts, and terminates the polymerizationreactions. The post reactor solution is then heated in preparation for atwo-stage devolatization. The solvent and unreacted monomers are removedduring the devolatization process. The polymer melt is pumped to a diefor underwater pellet cutting.

Polymer Examples 20-23 were made using similar procedures as describedin the above. Process details and results are contained in Tables 8A-C.Selected polymer properties are provided in Tables 9A-B. Table 9C showsthe block indices for various polymers measured and calculated accordingthe methodology described above. For calculations performed herein,T_(A) is 372° K, P_(A) is 1.

TABLE 8A Polymerization Conditions for Polymers 19A-J Cat A1² Cat A1 CatB2³ Cat B2 DEZ DEZ Cocat 1 Cocat 1 Cocat 2 Cocat 2 [Zn]⁴ in C₂H₄ C₈H₁₆Solv. H₂ T Conc. Flow Conc. Flow Conc Flow Conc. Flow Conc. Flow polymerEx. lb/hr lb/hr lb/hr sccm¹ ° C. ppm lb/hr ppm lb/hr wt % lb/hr ppmlb/hr ppm lb/hr ppm 19A 55.29 32.03 323.03 101 120 600 0.25 200 0.42 3.00.70 4500 0.65 525 0.33 248 19B 53.95 28.96 325.3 577 ″ ″ 0.25 ″ 0.553.0 0.24 ″ 0.63 ″ 0.11 90 19C 55.53 30.97 324.37 550 ″ ″ 0.216 ″ 0.6093.0 0.69 ″ 0.61 ″ 0.33 246 19D 54.83 30.58 326.33 60 ″ ″ 0.22 ″ 0.63 3.01.39 ″ 0.66 ″ 0.66 491 19E 54.95 31.73 326.75 251 ″ ″ 0.21 ″ 0.61 3.01.04 ″ 0.64 ″ 0.49 368 19F 50.43 34.80 330.33 124 ″ ″ 0.20 ″ 0.60 3.00.74 ″ 0.52 ″ 0.35 257 19G 50.25 33.08 325.61 188 ″ ″ 0.19 ″ 0.59 3.00.54 ″ 0.51 ″ 0.16 194 19H 50.15 34.87 318.17 58 ″ ″ 0.21 ″ 0.66 3.00.70 ″ 0.52 ″ 0.70 259 19I 55.02 34.02 323.59 53 ″ ″ 0.44 ″ 0.74 3.01.72 ″ 0.70 ″ 1.65 600 ¹standard cm³/min²[N-2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dimethyl ⁴ppm in final product calculated by mass balance

TABLE 8B Additional Polymerization Conditions for Polymers 19A-J PolyRate⁵ Conv⁶ Polymer [Zn]/[C₂H₄] * Ex. lb/hr wt % wt % [C₂H₄]/[Zn]⁷ 1000⁸Eff.⁹ 19A 83.94 88.0 17.28 775 1.29 297 19B 80.72 88.1 17.2 2222 0.45295 19C 84.13 88.9 17.16 775 1.29 293 19D 82.56 88.1 17.07 395 2.53 28019E 84.11 88.4 17.43 513 1.95 288 19F 85.31 87.5 17.09 725 1.38 319 19G83.72 87.5 17.34 1000 1.0 333 19H 83.21 88.0 17.46 752 1.33 312 19I86.63 88.0 17.6 317 3.15 275 ⁵polymer production rate ⁶weight percentethylene conversion in reactor ⁷molar ratio in reactor; Zn/C₂ * 1000 =(Zn feed flow * Zn concentration/1000000/Mw of Zn)/(Total Ethylene feedflow * (1 − fractional ethylene conversion rate)/Mw of Ethylene) * 1000.Please note that “Zn” in “Zn/C₂ * 1000” refers to the amount of zinc indiethyl zinc (“DEZ”) used in the polymerization process, and “C2” refersto the amount of ethylene used in the polymerization process. ⁸molarratio in reactor ⁹efficiency, lb polymer/lb M where lb M = lb Hf + lb Z

TABLE 8C Polymerization Conditions for Polymers 20-23. Cat Cat A1 CatCat B2 DEZ DEZ Co.* Solv. H₂ T A1² Flow B2³ Flow Conc. Flow Ex. Co.*Type kg/hr kg/hr sccm¹ ° C. ppm kg/hr ppm Kg/hr ppm Zn kg/hr 20 Octene1.6 11.4 104.8 119 71.7 0.059 46.4 0.055 1688 0.018 21 Butene ″ 10.5 9.9120 94.2 0.065 10.5 0.100 9222 0.068 22 Butene ″ 10.5 37.5 ″ ″ 0.064 ″0.088 ″ 0.018 23 Propylene 1.4 9.8 4.9 ″ 53.1 0.024 58.1 0.098 30300.151 Cocat Cocat [Zn]/ Poly Conc. Flow [C₂H₄]/ [C₂H₄] * Rate⁶ Conv⁷Solids Ex. ppm kg/hr [Zn]⁴ 1000⁵ kg/hr % % Eff.⁸ 20 1743 0.118 9166 0.111.6 90 11.4 239 21 1168 0.057 442 2.26 1.7 90.5 12.2 235 22 ″ 0.054 18510.54 1.6 90 11.9 228 23 429.4 0.139 1030 0.97 1.1 82.5 9.4 184 *“Co.”stands for “comonomer”. ¹standard cm3/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl ⁴molar ratio in reactor; Zn/C₂ * 1000 = (Zn feedflow * Zn concentration/1000000/Mw of Zn)/(Total Ethylene feed flow * (1− fractional ethylene conversion rate)/Mw of Ethylene) * 1000. Pleasenote that “Zn” in “Zn/C₂ * 1000” refers to the amount of zinc in diethylzinc (“DEZ”) used in the polymerization process, and “C2” refers to theamount of ethylene used in the polymerization process. ⁵molar ratio inreactor ⁶polymer production rate ⁷percent ethylene conversion in reactor⁸efficiency, kg polymer/g M where g M = g Hf + g Zr

TABLE 9A Polymer Physical Properties CRYSTAF Density Mw Mn Mw/ Heat ofT_(m) T_(c) T_(CRYSTAF) T_(m) − T_(CRYSTAF) Peak Ex. (g/cc) I₂ I₁₀I₁₀/I₂ (g/mol) (g/mol) Mn Fusion (J/g) (° C.) (° C.) (° C.) (° C.) Area(wt %) 19A 0.8781 0.9 6.4 6.9 123700 61000 2.0 56 119 97 46 73 40 19B0.8749 0.9 7.3 7.8 133000 44300 3.0 52 122 100 30 92 76 19C 0.8753 5.638.5 6.9 81700 37300 2.2 46 122 100 30 92  8 19D 0.8770 4.7 31.5 6.780700 39700 2.0 52 119 97 48 72  5 19E 0.8750 4.9 33.5 6.8 81800 417002.0 49 121 97 36 84 12 19F 0.8652 1.1 7.5 6.8 124900 60700 2.1 27 119 8830 89 89 19G 0.8649 0.9 6.4 7.1 135000 64800 2.1 26 120 92 30 90 90 19H0.8654 1.0 7.0 7.1 131600 66900 2.0 26 118 88 — — — 19I 0.8774 11.2 75.26.7 66400 33700 2.0 49 119 99 40 79 13

TABLE 9B Polymer Physical Properties of Compression Molded FilmsImmediate Immediate Immediate Set after Set after Set after Melt 100%300% 500% Recovery after Recovery after Recovery after Density IndexStrain Strain Strain 100% 300% 500% Example (g/cm³) (g/10 min) (%) (%)(%) (%) (%) (%) 19A 0.878 0.9 15 63 131  85 79 74 19B 0.877 0.88 14 4997 86 84 81 19F 0.865 1 — — 70 — 87 86 19G 0.865 0.9 — — 66 — — 87 19H0.865 0.92 — 39 — — 87 —

TABLE 9C Block Index for Selected Polymers Average Block Index (“BI”)Second Moment About the Mean Density I₂ Weight Weight Average ExampleComonomer (g/cc) g/10 min. Zn/C₂H₄ * 1000 Average BI BI F* Octene 0.88950.9 0 0 0 L* Octene 0.905 0.8 — 0 0.01 M* Octene 0.902 1.0 — 0 0 20Octene 0.8841 1.0 0.11 0.2 0.45  8 Octene 0.8828 0.9 0.56 0.59 0.32 19AOctene 0.8781 0.9 1.3 0.62 0.17  5 Octene 0.8786 1.5 2.4 0.53 0.136 19BOctene 0.8749 0.9 0.45 0.54 0.35 19I Octene 0.8774 11.2 3.15 0.59 0.2221 Butene 0.8795 0.9 1.89 0.65 0.22 22 Butene 0.8802 1.1 1.71 0.66 0.3323 Propylene 0.883 1.2 0.97 0.61 0.24 1) L* is a ultra low densitypolyethylene made by Ziegler-Natta catalysis and available from The DowChemical Company under the trademark of ATTANE ™ 4203. 2) M* is apolyethylene copolymer made by constrained geometry catalysis (i.e.,single-site catalyst) and available from The Dow Chemical Company underthe trademark of AFFINITY ® PL1880G.

As shown in Table 9C, all the inventive polymers have a weight averageblock index of greater than zero, whereas the random copolymers(Polymers F*, L*, and M*) all have a block index of zero.

FIG. 10 shows the block index distribution for Polymer F*, Polymer 20,Polymer 8, and Polymer 5 as a function of the ATREF temperature. ForPolymer F*, the block index for all the ATREF fraction is zero orsubstantially zero (i.e., ≦0.01). Polymer 20 was made with a relativelylow level of the shuttling agent, diethyl zinc (“DEZ”). While the weightaverage block index for the whole polymer is about 0.2, the polymerincludes four fractions with a block index from about 0.7 to about 0.9.For Polymers 5 and 8, their weight average block indices are notdrastically different (0.52 vs. 0.59), considering the DEZ level isabout a four-fold difference. Moreover, most of their fractions have ablock index of about 0.6 or higher. Similar results are seen betweenPolymer 5 and Polymer 19B, which is illustrated in FIG. 11. However,there are some notable differences in the block index for the fractionswhich elute from about 70° C. to about 90° C. Polymer 19B was made witha higher level (about four fold higher) of DEZ than Polymer 5. However,Polymer 5 has more fractions that have higher block indices. This seemsto suggest that there might be an optimal DEZ level for making fractionswith higher block indices (i.e., greater than about 0.6).

The effect of the DEZ concentration level on the average block index forsome of the polymers in Table 9C is illustrated in FIG. 12. The plotsseem to suggest that the average block index increases with increasingDEZ initially. Once Zn/C₂H₄*1000 exceeds about 0.5, the average blockindex appears to level off and may even drop off if too much DEZ isused.

FIG. 13 is a plot of the square root of the second moment about the meanweight average block index as a function of [Zn/C₂H₄]*1000. It appearsto decrease as DEZ increases. This would indicated that the distributionof the block indices of the fractions are becoming narrower (i.e., morehomogeneous).

TREF and NMR Data

Tables 10-14 list TREF, DSC, IR, and NMR data for Polymers 5, 8, 14, and19 and various comparative polymers.

TABLE 10 TREF Fractions from Ziegler-Natta LLDPE Mol % DeltaHFractionation ATREF T Octene Tm melt Temperature (° C.) (NMR) (° C.)(J/g) 35-40 49 8.0 82 84 40-45 56.5 7.0 86 97 45-50 57.5 6.6 89 10150-55 61 6.0 92 96 55-60 63.5 5.4 95 99 60-65 67.5 4.9 98 104 65-70 724.3 101 112 70-75 75.5 3.7 104 112 75-80 79 3.1 107 122 80-85 83.5 2.5112 131 85-90 90 1.7 116 154 90-95 95.5 1.1 123 160  95-100 100 0.5 128185 100-105 101 0.2 130 195 Ex. L * - Ziegler-Natta Example (Attane ™4203, 0.90 g/cm³, 0.8 I₂)

TABLE 11 TREF Fractions from Random Copolymer Mol % DeltaH FractionationATREF T Octene Tm melt Temperature (° C.) (NMR) (° C.) (J/g) 35-40 51.5NM 83 102 40-45 56 7.3 87 96 45-50 61.5 6.5 90 101 50-55 63.5 5.7 93 10055-60 66.5 5.3 95 104 60-65 69.5 4.9 97 105 65-70 72 4.4 99 111 70-75 744.2 101 111 75-80 76.5 3.8 106 112 Ex. M* - Random Copolymer Example(AFFINITY ® PL1880, 0.90 g/cm³, 1 I₂)

TABLE 12 TREF Fractions from Inventive Example 5 Inventive Example 5 Mol% DeltaH Fractionation ATREF T Octene Tm melt Temperature (° C.) (NMR)(° C.) (J/g) 60-65 70.5 12.6 106 45 65-70 73 12.2 108 48 70-75 77 11.7111 51 75-80 81 10.5 113 57 80-85 84 9.8 115 68 85-90 88.5 7.0 119 8390-95 92 5.2 123 110

TABLE 13 TREF Fractions from Inventive Example 8 Inventive Example 8 Mol% DeltaH Fractionation ATREF T Octene Tm melt Temperature (° C.) (NMR)(° C.) (J/g) 50-55 20 16.5 98 28 55-60 57.5 16.2 104 29 60-65 61.5 16.5106 28 65-70 65.5 16.2 109 29 70-75 70.5 15.7 112 31 75-80 73 15.5 11432 80-85 81.5 11.6 117 37 85-90 89.5 10.7 120 58 90-95 96 4.6 126 125 95-100 96.5 1.5 129 180

TABLE 14 ATREF Peak comonomer composition for random copolymers andExamples 5, 8, 14, 19 Mol % Infra-red Octene FWHM Mol % TREF Infra-redInfra-red CH₃/CH₂ Density Octene T_(ATREF) Peak FWHM FWHM Area Example(g/cc) I2 (NMR) (° C.) (Infra-red) CH₂ Area CH₃ Area Ratio N* 0.96 1.0 0102 0.0 37.5 28.2 0.753 O* 0.9371 2.0 0.69 95 1.2 29.0 22.2 0.765 M*0.9112 1.0 3.88 79 4.0 77.5 61.0 0.786 P* 0.9026 1.1 5.57 70 5.1 74.359.0 0.794 Q* 0.8872 0.9 9.06 57 9.2 30.9 25.5 0.824 Ex. 5 0.8786 1.5 NA82 11.4 77.5 61.0 0.841 Ex. 8 0.8828 0.9 NA 90 12.2 34.0 28.8 0.846 Ex.14 0.9116 2.6 NA 92 6.5 23.4 18.8 0.805 Ex. 19 0.9344 3.4 NA 97 2.8 25.319.7 0.777 Infra-red detector calibration: Mol % Octene = 133.38 (FWHMCH₃/CH₂ Area) − 100.8 N* is an ethylene homopolymer. O* is anethylene/octene copolymer available from The Dow Chemical Company underAFFINITY ® HF1030. P* is an ethylene/octene copolymer available from TheDow Chemical Company under AFFINITY ® PL1880. Q* is an ethylene/octenecopolymer available from The Dow Chemical Company under AFFINITY ®VP8770.

Calculation of Block Index

With reference to FIGS. 2-3, the calculation of block indices isexemplified for Polymer 5. In the calculations, the followingcalibration equation is used:

LnP=−237.8341/T _(ATREF)+0.6390

where P is the ethylene mole fraction, and T_(ATREF) is the ATREFelution temperature. In addition, the following parameters are used:

Parameter Value Explanation T_(A) 372.15 Analytical TREF elutiontemperature (° K) of hard segment P_(A) 1.000 Mole fraction of ethyleneof hard segment P_(AB) 0.892 Mole fraction of ethylene of whole polymerT_(AB) 315.722 Calculated equivalent analytical TREF elution temperature(° K) of whole polymer from whole polymer ethylene content

Table 15 gives details of the calculations for Polymer 5. The weightedaverage block index, ABI, for Polymer 5, is 0.531, and the square rootof sum of weighted squared deviations about the weighted mean is 0.136.The partial sum of weights with fraction BI greater than zero (see note2 below) is 0.835.

Measurement of Weight Percent of Hard and Soft Segments

As discussed above, the block interpolymers comprise hard segments andsoft segments. The soft segments can be present in a block interpolymerfrom about 1 weight percent to about 99 weight percent of the totalweight of the block interpolymer, preferably from about 5 weight percentto about 95 weight percent, from about 10 weight percent to about 90weight percent, from about 15 weight percent to about 85 weight percent,from about 20 weight percent to about 80 weight percent, from about 25weight percent to about 75 weight percent, from about 30 weight percentto about 70 weight percent, from about 35 weight percent to about 65weight percent, from about 40 weight percent to about 60 weight percent,or from about 45 weight percent to about 55 weight percent. Conversely,the hard segments can be present in a similar range as above. The softsegment weight percentage (and thus the hard segment weight percentage)can be measured by DSC or NMR.

TABLE 15 Fractional Block Index (BI) Calculations Random EquivalentATREF Random Temperature Equivalent Weighted from mole FractionalFractional Squared NMR fraction Block Block Index Deviations ATREF MoleEthylene ethylene Index based on Weighted about Elution Fraction WeightWeight from based on Log_(e) of mole Fractional the Temperature EthyleneFraction Fraction ATREF Temperature fraction Block Weighted Weight (° K)(NMR) Recovered (° K) Temperature formula formula Indices Mean (Note 2)Recovered Array Variable Name Fraction # (g) T_(x) P_(x) w_(i) T_(X0)P_(X0) BI_(i) BI_(i) w_(i) * BI_(i) w_(i) * (BI_(i) − ABI) 1 3.0402(Note 1) 0.859 0.165 (Note 1) (Note 1) 0 0 0 (Note 1) 2 1.9435 340 0.8730.106 307 0.941 0.659 0.659 0.070 0.0017 3 0.7455 343.5 0.883 0.041 3120.948 0.622 0.622 0.025 0.0003 4 1.0018 346 0.882 0.054 311 0.953 0.6760.676 0.037 0.0011 5 2.3641 350 0.896 0.128 318 0.960 0.607 0.607 0.0780.0007 6 4.1382 354 0.895 0.225 317 0.968 0.684 0.684 0.154 0.0052 73.5981 357 0.902 0.195 320 0.973 0.665 0.665 0.130 0.0035 8 1.2280 361.50.930 0.067 334 0.981 0.470 0.470 0.031 0.0003 9 0.3639 365 0.948 0.020343 0.987 0.357 0.357 0.007 0.0006 ABI 18.4233 Total Weight 1.000Normalization Weighted Sums 0.531 0.0135 check (Note 1): Fraction #1does not crystallize in the analytical ATREF and is assigned BI_(i) = 0(Note 2): The weighted squared deviations about the weighted mean useonly BI_(i) > 0

Hard Segment Weight Fraction Measured by DSC

For a block polymer having hard segments and soft segments, the densityof the overall block polymer, ρ_(overall), satisfies the followingrelationship:

$\frac{1}{\rho_{overall}} = {\frac{x_{hard}}{\rho_{hard}} + \frac{x_{soft}}{\rho_{soft}}}$

where ρ_(hard), and ρ_(soft), are the theoretical density of the hardsegments and soft segments, respectively. χ_(hard), and χ_(soft), arethe weight fraction of the hard segments and soft segments, respectivelyand they add up to one. Assuming ρ_(hard) is equal to the density ofethylene homopolymer, i.e., 0.96 g/cc, and transposing the aboveequation, one obtains the following equation for the weight fraction ofhard segments:

$x_{h} = \frac{\frac{1}{\rho_{overall}} - \frac{1}{\rho_{soft}}}{{- \frac{1}{\rho_{overall}}} + \frac{1}{0.96\mspace{14mu} g\text{/}{cc}}}$

In the above equation, ρ_(overall) can be measured from the blockpolymer. Therefore, if ρ_(soft) is known, the hard segment weightfraction can be calculated accordingly. Generally, the soft segmentdensity has a linear relationship with the soft segment meltingtemperature, which can be measured by DSC over a certain range:

ρ_(soft) =A*T _(m) +B

where A and B are constants, and T_(m) is the soft segment meltingtemperature in degrees Celsius. A and B can be determined by running DSCon various copolymers with a known density to obtain a calibrationcurve. It is preferable to create a soft segment calibration curve thatspan the range of composition (both comonomer type and content) presentin the block copolymer. In some embodiments, the calibration curvesatisfies the following relationship:

ρ_(soft)=0.00049*T _(m)+0.84990

Therefore, the above equation can be used to calculate the soft segmentdensity if T_(m) in degrees Celsius is known.

For some block copolymers, there is an identifiable peak in DSC that isassociated with the melting of the soft segments. In this case, it isrelatively straightforward to determine T_(m) for the soft segments.Once T_(m) in degrees Celsius is determined from DSC, the soft segmentdensity can be calculated and thus the hard segment weight fraction.

For other block copolymers, the peak associated with the melting of thesoft segments is either a small hump (or bump) over the baseline orsometimes not visible as illustrated in FIG. 14. This difficulty can beovercome by converting a normal DSC profile into a weighted DSC profileas shown in FIG. 15. The following method is used to convert a normalDSC profile to a weighted DSC profile.

In DSC, the heat flow depends on the amount of the material melting at acertain temperature as well as on the temperature-dependent specificheat capacity. The temperature-dependence of the specific heat capacityin the melting regime of linear low density polyethylene leads to anincrease in the heat of fusion with decreasing comonomer content. Thatis, the heat of fusion values get progressively lower as thecrystallinity is reduced with increasing comonomer content. See Wild, L.Chang, S.; Shankernarayanan, M J. Improved method for compositionalanalysis of polyolefins by DSC. Polym. Prep 1990; 31: 270-1, which isincorporated by reference herein in its entirety.

For a given point in the DSC curve (defined by its heat flow in wattsper gram and temperature in degrees Celsius), by taking the ratio of theheat of fusion expected for a linear copolymer to thetemperature-dependent heat of fusion (ΔH(T)), the DSC curve can beconverted into a weight-dependent distribution curve.

The temperature-dependent heat of fusion curve can be calculated fromthe summation of the integrated heat flow between two consecutive datapoints and then represented overall by the cumulative enthalpy curve.

The expected relationship between the heat of fusion for linearethylene/octene copolymers at a given temperature is shown by the heatof fusion versus melting temperature curve. Using random ethylene/octenecopolymers, one can obtain the following relationship:

Melt Enthalpy(J/g)=0.0072*T _(m) ²(° C.)+0.3138*T _(m)(° C.)+8.9767

For each integrated data point, at a given temperature, by taking aratio of the enthalpy from the cumulative enthalpy curve to the expectedheat of fusion for linear copolymers at that temperature, fractionalweights can be assigned to each point of the DSC curve.

It should be noted that, in the above method, the weighted DSC iscalculated in the range from 0° C. until the end of melting. The methodis applicable to ethylene/octene copolymers but can be adapted to otherpolymers.

Applying the above methodology to various polymers, the weightpercentage of the hard segments and soft segments were calculated, whichare listed in Table 16. It should be noted that sometimes it isdesirable to assign 0.94 g/cc to the theoretical hard segment density,instead of using the density for homopolyethylene, due to the fact thatthe hard segments may include a small amount of comonomers.

TABLE 16 Calculated Weight Percentage of Hard and Soft Segments forVarious Polymers Soft Segment Calculated Polymer T_(m) (° C.) from SoftCalculated Calculated Example Overall weighted Segment wt % Hard wt %Soft No. Density DSC Density Segment Segment F* 0.8895 20.3 0.860 32%68%  5 0.8786 13.8 0.857 23% 77%  6 0.8785 13.5 0.857 23% 77%  7 0.882516.5 0.858 26% 74%  8 0.8828 17.3 0.858 26% 74%  9 0.8836 17.0 0.858 27%73% 10 0.878 15.0 0.857 22% 78% 11 0.882 16.5 0.858 25% 75% 12 0.87019.5 0.859 12% 88% 13 0.872 23.0 0.861 12% 88% 14 0.912 21.8 0.861 54%46% 15 0.8719 0.5 0.850 22% 78% 16 0.8758 0.3 0.850 26% 74% 18 0.9192 —— — — 19 0.9344 38.0 0.869 74% 26% 17 0.8757 2.8 0.851 25% 75% 19A0.8777 11.5 0.856 23% 77% 19B 0.8772 14.3 0.857 22% 78%

Hard Segment Weight Percentage Measured by NMR

¹³C NMR spectroscopy is one of a number of techniques known in the artfor measuring comonomer incorporation into a polymer. An example of thistechnique is described for the determination of comonomer content forethylene/α-olefin copolymers in Randall (Journal of MacromolecularScience, Reviews in Macromolecular Chemistry and Physics, C29 (2 & 3),201-317 (1989)), which is incorporated by reference herein in itsentirety. The basic procedure for determining the comonomer content ofan ethylene/olefin interpolymer involves obtaining a ¹³C NMR spectrumunder conditions where the intensity of the peaks corresponding to thedifferent carbons in a sample is directly proportional to the totalnumber of contributing nuclei in the sample. Methods for ensuring thisproportionality are known in the art and involve allowance forsufficient time for relaxation after a pulse, the use ofgated-decoupling techniques, relaxation agents, and the like. Therelative intensity of a peak or group of peaks is obtained in practicefrom its computer-generated integral. After obtaining the spectrum andintegrating the peaks, those peaks associated with the comonomer areassigned. This assignment can be made by reference to known spectra orliterature, or by synthesis and analysis of model compounds, or by theuse of isotopically labeled comonomers. The mole % comonomer can bedetermined by the ratio of the integrals corresponding to the number ofmoles of comonomer to the integrals corresponding to the number of molesof all of the monomers in the interpolymer, as described in theaforementioned Randall reference.

Since the hard segment generally has less than about 2.0 wt % comonomer,its major contribution to the spectrum is only for the integral at about30 ppm. The hard segment contribution to the peaks not at 30 ppm isassumed negligible at the start of the analysis. So for the startingpoint, the integrals of the peaks not at 30 ppm are assumed to come fromthe soft segment only. These integrals are fit to a first orderMarkovian statistical model for copolymers using a linear least squaresminimization, thus generating fitting parameters (i.e., probability ofoctene insertion after octene, P_(oo), and probability of octeneinsertion after ethylene, P_(eo)) that are used to compute the softsegment contribution to the 30 ppm peak. The difference between thetotal measured 30 ppm peak integral and the computed soft segmentintegral contribution to the 30 ppm peak is the contribution from thehard segment. Therefore, the experimental spectrum has now beendeconvoluted into two integral lists describing the soft segment andhard segment, respectively. The calculation of weight percentage of thehard segment is straight forward and calculated by the ratio of the sumof integrals for the hard segment spectrum to the sum of integrals forthe overall spectrum.

From the deconvoluted soft segment integral list, the comonomercomposition can be calculated according to the method of Randall, forexample. From the comonomer composition of the overall spectrum and thecomonomer composition of the soft segment, one can use mass balance tocompute the comonomer composition of the hard segment. From thecomonomer composition of the hard segment, Bernoullian statistics isused to calculate the contribution of the hard segment to the integralsof non 30 ppm peaks. There is usually so little octene, typically fromabout 0 to about 1 mol %, in the hard segment that Bernoullianstatistics is a valid and robust approximation. These contributions arethen subtracted out from the experimental integrals of the non 30 ppmpeaks. The resulting non 30 ppm peak integrals are then fitted to afirst order Markovian statistics model for copolymers as described inthe above paragraph. The iterative process is performed in the followingmanner: fit total non 30 ppm peaks then compute soft segmentcontribution to 30 ppm peak; then compute soft/hard segment split andthen compute hard segment contribution to non 30 ppm peaks; then correctfor hard segment contribution to non 30 ppm peaks and fit resulting non30 ppm peaks. This is repeated until the values for soft/hard segmentsplit converge to a minimum error function. The final comonomercompositions for each segment are reported.

Validation of the measurement is accomplished through the analysis ofseveral in situ polymer blends. By design of the polymerization andcatalyst concentrations the expected split is compared to the measuredNMR split values. The soft/hard catalyst concentration is prescribed tobe 74%/26%. The measured value of the soft/hard segment split is78%/22%. Table 17 shows the chemical shift assignments for ethyleneoctene polymers.

TABLE 17 Chemical Shift Assignments for Ethylene/Octene Copolymers.  41-40.6 ppm OOOE/EOOO αα CH2 40.5-40.0 ppm EOOE αα CH2 38.9-37.9 ppmEOE CH 36.2-35.7 ppm OOE center CH 35.6-34.7 ppm OEO αγ, OOO center 6B,OOEE αδ+, OOE center 6B CH2 34.7-34.1 ppm EOE αδ+, EOE 6B CH2 33.9-33.5ppm OOO center CH 32.5-32.1 ppm 3B CH2 31.5-30.8 ppm OEEO γγ CH230.8-30.3 ppm OE γδ+ CH2 30.3-29.0 ppm 4B, EEE δ+δ+ CH2 28.0-26.5 ppm OEβδ+ 5B 25.1-23.9 ppm OEO ββ 23.0-22.6 ppm 2B 14.5-14.0 ppm 1B

The following experimental procedures are used. A sample is prepared byadding 0.25 g in a 10 mm NMR tube with 2.5 mL of stock solvent. Thestock solvent is made by dissolving 1 g perdeuterated1,4-dichlorobenzene in 30 mL ortho-dichlorobenzene with 0.025 M chromiumacetylacetonate (relaxation agent). The headspace of the tube is purgedof oxygen by displacement with pure nitrogen. The sample tube is thenheated in a heating block set at 150° C. The sample tube is repeatedlyvortexed and heated until the solution flows consistently from top ofthe solution column to the bottom. The sample tube is then left in theheat block for at least 24 hours to achieve optimum sample homogeneity.

The ¹³C NMR data is collected using a Varian Inova Unity 400 MHz systemwith probe temperature set at 125° C. The center of the excitationbandwidth is set at 32.5 ppm with spectrum width set at 250 ppm.Acquisition parameters are optimized for quantitation including 90°pulse, inverse gated ¹H decoupling, 1.3 second acquisition time, 6seconds delay time, and 8192 scans for data averaging. The magneticfield is carefully shimmed to generate a line shape of less than 1 Hz atfull width half maximum for the solvent peaks prior to data acquisition.The raw data file is processed using NUTS processing software (availablefrom Acorn NMR, Inc. in Livermore, Calif.) and a list of integrals isgenerated.

Inventive Polymer 19A is analyzed for the soft/hard segment split andsoft/hard comonomer composition. The following is the list of integralsfor this polymer. The NMR spectrum for Polymer 19A is shown in FIG. 16.

Integral limit Integral value 41.0-40.6 ppm 1.067 40.5-40.0 ppm 6.24738.9-37.9 ppm 82.343 36.2-35.7 ppm 14.775 35.6-34.7 ppm 65.563 34.7-34.1ppm 215.518 33.9-33.5 ppm 0.807 32.5-32.1 ppm 99.612 31.5-30.8 ppm14.691 30.8-30.3 ppm 115.246 30.3-29.0 ppm 1177.893 28.0-26.5 ppm258.294 25.1-23.9 ppm 19.707 23.0-22.6 ppm 100 14.5-14.0 ppm 99.895

Using Randall's triad method, the total octene weight percentage in thissample is determined to be 34.6%. Using all the above integralsexcluding the 30.3-29.0 ppm integral to fit a first order Markovianstatistical model, the values for P_(oo) and P_(eo) are determined to be0.08389 and 0.2051, respectively. Using these two parameters, thecalculated integral contribution from the soft segment to the 30 ppmpeak is 602.586. Subtraction of 602.586 from the observed total integralfor the 30 ppm peak, 1177.893, yields the contribution of the hardsegment to the 30 ppm peak of 576.307. Using 576.307 as the integral forthe hard segment, the weight percentage of hard segment is determined tobe 26%. Therefore the soft segment weight percentage is 100−26=74%.Using the above values for P_(oo) and P_(eo), the octene weightpercentage of the soft segment is determined to be 47%. Using theoverall octene weight percentage and the octene weight percentage of thesoft segment as well as the soft segment weight percentage, the octeneweight percentage in the hard segment is calculated to be negative 2 wt%. This value is within the error of the measurement. Thus there is noneed to iterate back to account for hard segment contribution to non 30ppm peaks. Table 18 summarizes the calculation results for Polymers 19A,B, F and G.

TABLE 18 Hard and Soft Segments Data for Polymers 19A, B, F and G wt %wt % wt % octene Soft Hard in Soft Example Segment Segment Segment 19A74 26 47 19B 74 26 48 19F  86 14 49 19G 84 16 49

Additional Examples Set 1

Examples 24-28 were prepared in a similar fashion as Examples 5-19.Table 19 shows the polymerization conditions for these examples andTable 20 shows the physical properties of these polymers.

TABLE 19 Polymerization Conditions for Examples 24-28 Cat Cat A1 Cat B2DEZ DEZ Cocat Cocat Poly C₈H₁₆ Solv. H₂ T A1² Flow B2³ Flow Conc FlowConc. Flow [C₂H₄]/ Rate⁵ Ex. kg/hr kg/hr sccm¹ ° C. ppm kg/hr ppm kg/hrppm Zn kg/hr ppm kg/hr [DEZ]⁴ kg/hr Conv %⁶ Solids % Eff.⁷ 24 15.82150.2 150 120 600 0.089 200 0.271 30000 0.335 4500 0.235 769 38.8 87.517.1 319 25 35.82 362.0 263 ″ 568 0.586 100 0.377 50000 0.259 5500 0.5821377 92.7 88.1 17.7 117 26 47.77 414.4 195 ″ ″ 0.864 ″ 1.111 ″ 0.370 ″0.968 1047 106 87.8 17.8 104 27 38.36 357.7 323 ″ ″ 0.636 ″ 0.682 150000.891 ″ 0.886 1282 93 89.3 17.8 112 28 14.52 146.52 101 ″ 600 0.113 2000.191 30000 0.318 4500 0.295 775 38.0 88.0 17.3 297 ¹standard cm3/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl ⁴molar ratio in reactor ⁵polymer production rate⁶percent ethylene conversion in reactor ⁷efficiency, kg polymer/g Mwhere g M = g Hf + g Zr

TABLE 20 Polymer Properties for Examples 24-28 Heat of Tm − Density MwMn Fusion T_(CRYSTAF) T_(CRYSTAF) CRYSTAF Peak Ex. (g/cm³) I₂ I₁₀ I₁₀/I₂(g/mol) (g/mol) Mw/Mn (J/g) T_(m) (° C.) T_(c) (° C.) (° C.) (° C.) Area(percent) 24 0.865 1.1 7.5 6.8 124900 60700 2.1 27 119 88 30 89 90 250.875 0.5 3.7 7.3 146900 66600 2.2 51 120 101 52 68 39 26 0.866 1.0 7.37.3 134900 63300 2.1 22 119 98 36 83 6 27 0.877 0.5 3.9 7.2 144500 694002.1 48 120 99 49 71 72 28 0.878 0.9 6.4 6.9 123700 61000 2.0 56 119 9751 67 31

Table 20 shows polymer properties for Examples 24-28, while Table 21shows comonomer levels in the polymers as measured by ¹³C NMR. Example24 has a difference in octene content in the hard and soft segments, orΔ Octene, of 16.7 mol %. Examples 25 and 26 have Δ Octene=17.5 mol %,Example 27 has Δ Octene=18.2 mol %, and Example 28 has A Octene=16.2 mol%. These samples all have I₁₀/I₂ values <7.3. The relationship betweenI₁₀/I₂ and Δ Octene is shown graphically in FIG. 17.

TABLE 21 Comonomer content Overall Octene Octene in Soft Octene in HardΔ Example (mol %) Segment (mol %) Segment (mol %) Octene 24 15.2 17.10.4 16.7 25 12.3 18.0 0.5 17.5 26 15.7 18.4 0.5 17.5 27 12.83 19.1 0.918.2 28 11.9 16.6 0.4 16.2

Additional Examples Set 2 Mesophase Separated Polymers

Examples 29-40 were prepared in a similar fashion as Examples 5-19.Table 22 shows the polymerization conditions for these examples andTable 23 shows the physical properties of these polymers. Some of thesepolymers exhibit a blueish tint via reflected light and appear yellowwhen viewed via transmitted light.

TABLE 22 Polymerization Conditions for Examples 29-40 DEZ Cat Cat A1 CatB2 Conc DEZ Cocat Cocat Poly C₈H₁₆ Solv. H₂ T A1² Flow B2³ Flow (ppmFlow Conc. Flow [C₂H₄]/ Rate⁵ Conv Solids Ex. kg/hr kg/hr sccm¹ ° C. ppmkg/hr ppm kg/hr Zn) kg/hr ppm kg/hr [DEZ]⁴ kg/hr %⁶ % Eff.⁷ 29 5.21 9.533 120 93.2  0.111 15.9 0.119 2690 0.086 952 0.111 2113 1.6 79.6 9.6 12830 5.24 9.89 0 ″ ″ 0.144 ″ 0.152 ″ 0.145 ″ 0.150 1147 1.9 84.4 11.3 12031 5.19 9.53 0 ″ 56.20 0.193 ″ 0.126 ″ 0.122   525.5 0.213 1725 1.6 79.99.9 127 32 5.19 9.52 8 ″ 93.20 0.092 ″ 0.097 ″ 0.060   951.5 0.093 29761.6 80.1 9.8 156 33 5.21 9.89 5 ″ ″ 0.128 ″ 0.135 ″ 0.112 ″ 0.126 13852.0 85.3 11.7 139 34 4.62 9.89 3 ″ 92.90 0.183 ″ 0.338 ″ 0.101 ″ 0.2141382 1.5 86.3 9.3 68 35 34.55 341.5 161 ″ 568    0.441 100   0.68250000  0.518 5500  0.314 693 92 88.9 17.6 131 36 33.55 340.3 290 ″ ″0.359 ″ 0.759 ″ 0.186 ″ 0.505 1518 92 89.3 17.4 148 37 37.55 313.8 136 ″″ 0.318 ″ 0.814 ″ 0.314 ″ 0.482 943 89 88.0 16.8 148 38 56.1 541.6 370 ″″ 0.508 ″ 0.590 ″ 0.377 5535  0.572 973 111.0 86.1 18.1 320 39 5.21 9.520 ″ 56.2  0.196 15.9 0.094 2690 0.126 526 0.203 1706 1.6 80.2 9.9 131 404.76 9.89 0 ″ 92.9  0.181 ″ 0.332 ″ 0.147 952 0.214 1042 1.6 85.6 9.7 74¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl ⁴molar ratio in reactor ⁵polymer production rate⁶percent ethylene conversion in reactor ⁷efficiency, kg polymer/g Mwhere g M = g Hf + g Zr

TABLE 23 Polymer Properties for Examples 29-40 Heat of Tm − Density MwMn Fusion T_(CRYSTAF) T_(CRYSTAF) CRYSTAF Peak Ex. (g/cm³) I₂ I₁₀ I₁₀/I₂(g/mol) (g/mol) Mw/Mn (J/g) T_(m) (° C.) T_(c) (° C.) (° C.) (° C.) Area(percent) 29 0.876 0.5 4.9 9.7 151500 70300 2.2 47 117 100 72 45 52 300.867 1.0 9.9 9.9 152000 56940 2.7 31 114 92 44 71 24 31 0.874 0.5 4.89.0 151200 68500 2.2 43 117 97 62 55 26 32 0.875 0.5 5.4 10.2 15740069600 2.3 44 118 101 73 44 18 33 0.866 1.1 11.7 10.5 157900 61640 2.6 26115 93 44 71 7 34 0.894 0.5 4.4 8.8 136000 66300 2.1 86 118 104 72 46 8635 0.889 1.1 7.8 6.9 110000 57800 1.9 70 120 102 61 59 53 36 0.888 0.96.7 7.7 126900 55100 2.3 69 122 104 75 47 44 37 0.884 0.9 7.3 7.9 13070058200 2.2 62 119 102 74 45 41 38 0.872 1.0 8.9 8.5 144000 72200 2.0 36118 96 73 46 10 39 0.871 0.7 6.0 9.1 154800 72800 2.1 47 116 97 59 57 3740 0.888 0.6 4.9 8.4 131000 63800 2.1 75 117 101 69 48 86

TABLE 24 Comonomer content for Examples 29-40 Overall Octene Octene inSoft Octene in Hard Δ Example (mol %) Segment (mol %) Segment (mol %)Octene 29 15.1 26 1.4 24.6 30 21.3 29.7 1.7 28.0 31 16.6 26.5 1.3 25.232 16.3 26.6 1.4 25.2 33 21.5 29.3 1.6 27.7 34 11.3 27.5 1.4 26.1 3510.8 20.9 0.7 20.2 36 11.0 22.4 0.9 21.5 37 12.8 25.8 1.1 24.7 38 18.026.0 1.2 24.8 39 17.2 26.1 1.4 24.7 40 11.6 29.2 1.6 27.6

One additional feature of this inventive block interpolymer is that itdisplayed an unusual shear thinning characteristic in the melt. At agiven melt index (I₂), some embodiments of the inventive blockinterpolymers with high α-olefin materials have higher molecular weightsand I₁₀/I₂ values than block interpolymers with lower α-olefin content.Examples 24-28 have Δ Octene <18.5 mol % and I₁₀/I₂<7.3. As seen inTable 24, Examples 29-40 all have Δ Octene >18.5 mol %. Example 35 has ΔOctene=20.2 and I₁₀/I₂=6.9, but the rest of the examples (Examples29-34, 36-40) have I₁₀/I₂≧7.7. This higher I₁₀/I₂ may be used todistinguish these examples from examples with Δ Octene <18.5 mol %.Differences in I₁₀/I₂ and Δ Octene for the samples is shown graphicallyin FIG. 17. The higher I₁₀/I₂ values indicate that the polymer underhigh shear stresses flows more readily than a block interpolymer withlow octene content. This enhanced flow may be useful for the coating ofpressure sensitive adhesives, for example, which requires easy flow; itmay also allow the use of higher molecular weight polymers in adhesiveformulations which may result in improved creep resistance and holdingpower.

Microscopy Studies Preparation of Compression Molded Samples

About 40 g of the polymer was compression molded into a 2 inch×2inch×0.06 inch plaque between Mylar sheets sandwiched between metalplatens in a Carver compression molding machine for 3 minutes at 190°C., 2 kpsi pressure for 3 minutes, 190° C., 20 kpsi pressure for 3minutes, then cooling at 15° C., 20 kpsi for 3 minutes.

Preparation of Examples 32-34 for AFM Study

Examples 32-34 were studied using tapping mode Atomic Force Microscopy(AFM). Compression molded samples were first polished using anultramicrotome (Reichert-Jung Ultracut E) at −120° C. perpendicular tothe plaques near the center of the core area. A thin section was placedon a mica surface for AFM imaging using a DI NanoScope IV, MultiMode AFMoperating in Tapping Mode with phase detection. The tip was tuned to avoltage of 3V and the tapping ratio was 0.76-0.83. Nano-sensor tips wereused with tip parameters of: L=235 μm, tip ratio=5-10 nm, Springconstant=37-55 N/m, F₀=159-164 kHz.

FIGS. 18-20 show images of Examples 32-34 taken via AFM at approximately3,000× magnification. These images show mesophase morphology similar toSBC morphology except for the size range of the observed domains; thedomains are much larger than those of a monodisperse block copolymerwith similar molecular weight. An example of an SBC polymer (28 wt %styrene, 83 mol % “butene” in the B-block, M_(n)=64,000 g/mol) atapproximately 30,000× magnification is shown in FIG. 21.

Preparation of Example 34 for TEM Study

Example 34 was studied using transmission electron microscopy (TEM). Thecompression molded sheets were trimmed so that sections could becollected between the skin and core. The trimmed sheets werecryopolished prior to staining by removing sections from the blocks at−60° C. to prevent smearing of the elastomer phases. The cryo-polishedblocks were stained with the vapor phase of a 2% aqueous rutheniumtetraoxide solution for 3 hrs at ambient temperature. The stainingsolution was prepared by weighing 0.2 gm of ruthenium (III) chloridehydrate (RuCl₃×H₂O) into a glass bottle with a screw lid and adding 10mL of 5.25% aqueous sodium hypochlorite to the jar. The samples wereplaced in the glass jar using a glass slide having double sided tape.The slide was placed in the bottle in order to suspend the blocks about1 inch above the staining solution. Sections of approximately 100nanometers in thickness were collected at ambient temperature using adiamond knife on a Leica EM UC6 microtome and placed on 400 mesh virginTEM grids for observation.

Images were collected on a JEOL JEM-1230 operated at 100 kV acceleratingvoltage and collected on a Gatan-791 and 794 digital cameras. The imageswere post processed using Adobe Photoshop 7.0. FIG. 22 shows a TEMmicrograph of Example 34 at approximately 30,000× magnification.

Preparation of Examples 29, 30, 32, and 33-40 for ReflectanceSpectroscopy Study

The reflectance spectra of Examples 29, 30, 32, and 33-40 were collectedwith a Labsphere™ (model 60MM RSA ASSY) integrating sphere. Spectralon™diffuse reflectance standards were first mounted on both sample andreference ports of integrating sphere and the baseline correction wasperformed for the spectral range from 200-1200 nm. The slit width andspectral resolution were 2 nm and the spectrum was acquired with 1nm/point. The Spectralon™ standard was then removed from the sample portand the film sample mounted in the sample port at a 90 degree incidenceangle to the sample beam. No backing material was used and the filmitself provided the only means of light reflectance.

FIGS. 23, 24 and 25 show the reflectance spectra of compression moldedfilms of Examples 35 thru 38, Examples 29, 30, 32 and 33 and Examples34, 39 and 40 respectively. A compression molded film of AFFINITY®PL1280G (available from The Dow Chemical Company)) is also provided ineach Figure for comparison. In contrast to the reflectance spectra ofthe film of the AFFINITY® material, which exhibits little or noreflection across the measured range of wavelengths, each of the Examplefilms exhibit a peak reflectance between 12 and 45% reflectivity. FIG.26 shows the reflectance spectra for Examples 25 and 26 which are notmesophase separated, which exhibit peak reflectances of less than about12%.

Physical Properties of Examples 26, 27, and 30-32.

The data presented in Table 25 demonstrates that at the same density,the mesophase separated materials have a lower Shore A and 100% secantmodulus than the samples with lower values of Δ octene. This same datais presented graphically in FIG. 27 which shows Shore A vs. density forExamples 26, 27, 30 and 31 and FIG. 28 which shows 100% Modulus vs.density for these same Examples. This shows that ethylene/α-olefin blockcopolymer-based materials may be made having a lower modulus or Shore Aat a given density. When compared at the same Shore A (Ex 26 and Ex 31),the mesophase separated material has a significantly lower 70° C. ASTMcompression set compared to the non-mesophase separated material (35%versus 64%). FIG. 29 shows 70° C. compression set vs. Shore A for theseExamples as well as Ex 27 and 30. The mesophase separated examples showcomparable permanent set as the non-phase separated materials at aboutthe same density when stretched to 300% strain.

TABLE 25 100% Shore A Secant 300% Density Hardness Modulus CompressionPermanent Example (g/cm³) (0.5 sc) (MPa) set (70° C.) Set (%) 26 0.86661 1.5 64 36 27 0.877 75 2.4 39 44 30 0.867 46 0.8 46 41 31 0.874 61 1.535 43

The dynamic mechanical relaxation responses as a function of temperatureare presented as Tan δ curves in FIGS. 30 and 31 for Examples 26 and 30and Examples 27 and 31, respectively. The glass transition, T_(g), fromthe Tan δ curve and intensity of the peak are tabulated in Table 26. Atsimilar density, the mesophase separated materials exhibit T_(g)'s thatare approximately 7° C. lower than non-mesophase separated materials. Alower Tg offers the advantage of lower useful temperature range whenused as an impact modifier.

TABLE 26 Example Density (g/cm³) Tg (° C.) Max tan δ 26 0.866 −48 0.4427 0.877 −45 0.45 30 0.867 −55 0.86 31 0.874 −52 0.55

FIG. 32 shows that the mesophase separated materials exhibit a similarlyflat storage modulus as exhibited by the non-mesophase separatedmaterials.

Blends with Oil and Polypropylene

Blend formulations using inventive Ex. 29 and Comp. Ex. 25 with oil andpolypropylene are listed in Table 27 together with Shore A and 70° C.compression set results. As also observed in Ex. 30 and Ex. 31, theinventive Ex 29 has lower Shore A than non-mesophase separated materialat similar density. The lower Shore A is also observed in blends withthe inventive example. This means that one can achieve softer blendsusing the mesophase separated material. FIG. 33 shows 70° C. CompressionSet vs Shore A for Blends 3, 4, 7 and 8. It is observed that blends withmesophase separated material result in a lower 70° C. Compression Set ata similar Shore A. In formulated soft compounds, one can achieve softermaterials with lower compression set when using the inventive polymer.

TABLE 27 Com- wt. % Wt. % Shore A pression Ex- Ex. 25 Ex. 29 wt. % wt. %Density Hardness set ample polymer polymer oil¹ hPP² (g/cc) (5 sec) (70°C.) Ex. 25 100 0 0 0 0.875 75 45 Ex. 29 0 100 0 0 0.876 61 35 Blend 1 350 50 15 53 64 Blend 2 28 0 60 12 31 60 Blend 3 0 35 50 15 31 54 Blend 40 28 60 12 19 53 ¹Chevron ParaLux 6001R Oil (Chevron U.S.A. Inc.)²Polypropylene H314-02Z (The Dow Chemical Company)

Block Index for Example 34

The weighted average block index, ABI, for Example 34, is 0.75, and thesquare root of sum of weighted squared deviations about the weightedmean is 1.12 (Table 28).

TABLE 28 Inventive Example 34 Wt Mol % DeltaH Fractional FractionationFraction ATREF Octene Tm melt Block Temperature Recovered T (° C.) (NMR)(° C.) (J/g) Index 20 0.0387 20 25.4 115.1 5.4 0 20-60 0.0154 53.5 22.4115.3 22.7 1.38 60-65 0.0126 63 20.8 105.2 32.4 1.39 65-70 0.0111 69.519.2 109.5 42.6 1.33 70-75 0.0199 75 18.3 112.3 48.5 1.33 75-80 0.049780.5 16.1 114.3 58.3 1.19 80-85 0.2059 87 12.4 114.7 72.4 0.93 85-900.4877 90 8.3 116.9 97.4 0.59 90-95 0.1585 93 4.4 120.0 127.2 0.28Weight Average 0.75 Block Index Square root of sum of weighted 1.12squared deviations about the weighted mean

FIG. 34 graphically shows that the heat of fusion (determined by DSC) ofATREF fractions of Example 34 are significantly lower than those ofATREF fractions of random ethylene octene copolymers (ATTANE® 4203, 0.90g/cm³, 0.8 I₂ and AFFINITY® PL1880, 0.90 g/cm³, 1 I₂—each available fromThe Dow Chemical Company). Specifically, the block interpolymer hasmolecular fractions which elute between 40° C. and 130° C., whenfractionated using TREF increments, that are characterized in that everyfraction that has an ATREF elution temperature greater than or equal toabout 76° C., has a melt enthalpy (heat of fusion) as measured by DSC,corresponding to the equation: Heat of fusion (J/gm)≦(3.1718)(ATREFelution temperature in Celsius)−136.58, while every fraction that has anATREF elution temperature between 40° C. and less than about 76° C., hasa melt enthalpy (heat of fusion) as measured by DSC, corresponding tothe equation: Heat of fusion (J/gm)≦(1.1312)(ATREF elution temperaturein Celsius)+22.97.

FIG. 35 graphically shows that the melting points of ATREF fractions ofExample 34 are significantly higher than those from ATREF fractions ofrandom ethylene octene copolymers (ATTANE® 4203, 0.90 g/cm³, 0.8 I₂ andAFFINITY® PL1880, 0.90 g/cm³, 1 I₂—each available from The Dow ChemicalCompany) that are fit to a line representing (−5.5926 (mol % comonomerof the ATREF fraction)+135.90 (solid line).

As demonstrated above, embodiments of the invention provide a new classof ethylene and α-olefin block interpolymers. The block interpolymersare characterized by an average block index of greater than zero,preferably greater than 0.2. Due to the block structures, the blockinterpolymers have a unique combination of properties or characteristicsnot seen for other ethylene/α-olefin copolymers. Moreover, the blockinterpolymers comprise various fractions with different block indices.The distribution of such block indices has an impact on the overallphysical properties of the block interpolymers. It is possible to changethe distribution of the block indices by adjusting the polymerizationconditions, thereby affording the abilities to tailor the desiredpolymers. Such block interpolymers have many end-use applications. Forexample, the block interpolymers can be used to make polymer blends,fibers, films, molded articles, lubricants, base oils, etc. Otheradvantages and characteristics are apparent to those skilled in the art.

While the invention has been described with respect to a limited numberof embodiments, the specific features of one embodiment should not beattributed to other embodiments of the invention. No single embodimentis representative of all aspects of the invention. In some embodiments,the compositions or methods may include numerous compounds or steps notmentioned herein. In other embodiments, the compositions or methods donot include, or are substantially free of, any compounds or steps notenumerated herein. Variations and modifications from the describedembodiments exist. The method of making the resins is described ascomprising a number of acts or steps. These steps or acts may bepracticed in any sequence or order unless otherwise indicated. Finally,any number disclosed herein should be construed to mean approximate,regardless of whether the word “about” or “approximately” is used indescribing the number. The appended claims intend to cover all thosemodifications and variations as falling within the scope of theinvention.

1. A composition comprising at least one ethylene/α-olefin blockinterpolymer, comprising one or more hard segments and one or more softsegments having a difference in mole percent α-olefin content, whereinthe ethylene/α-olefin block interpolymer is characterized by a molecularweight distribution, M_(w)/M_(n), in the range of from about 1.4 toabout 2.8 and by an average block index greater than zero and up toabout 1.0; and, wherein the ethylene/α-olefin block interpolymer ismesophase separated.
 2. (canceled)
 3. (canceled)
 4. An ethylene/α-olefinblock interpolymer comprising one or more hard segments and one or moresoft segments having a difference in mole percent α-olefin contentwherein the copolymer is characterized by an average molecular weight ofgreater than 40,000 g/mol, a molecular weight distribution, Mw/Mn, inthe range of from about 1.4 to about 2.8, and a difference in molepercent α-olefin content between the soft segment and the hard segmentof greater than about 18.5 mole percent.
 5. The ethylene/α-olefin blockinterpolymer of claim 1 wherein the ethylene/α-olefin block copolymercomprises domains wherein the domains have a smallest dimension in therange of from about 40 nm to about 300 nm.
 6. The ethylene/α-olefinblock interpolymer of claim 1, wherein the α-olefin is styrene,propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene,1-decene, 1,5-hexadiene, or a combination thereof.
 7. Theethylene/α-olefin block interpolymer of claim 6 wherein the α-olefin isoctene and the difference in mole percent α-olefin content between thehard segment and soft segment is greater than about 20.0 mole percent.8. (canceled)
 9. The ethylene/α-olefin block interpolymer of claim 6wherein the α-olefin is propylene and the difference in mole percentα-olefin content between the hard segment and soft segment is greaterthan about 40.7 mole percent.
 10. The ethylene/α-olefin blockinterpolymer of claim 1 wherein the ethylene/α-olefin block copolymerhas been compression molded.
 11. (canceled)
 12. (canceled) 13.(canceled)
 14. (canceled)
 15. (canceled)
 16. (canceled)
 17. (canceled)18. The ethylene/α-olefin block interpolymer of claim 1, wherein theblock copolymer has a density of less than about 0.91 g/cc.
 19. Theethylene/α-olefin block interpolymer of claim 18, wherein theinterpolymer has a density in the range from about 0.86 g/cc to about0.91 g/cc.
 20. (canceled)
 21. (canceled)
 22. (canceled)
 23. (canceled)24. The ethylene/α-olefin block interpolymer of claim 1, wherein theethylene/α-olefin interpolymer is characterized by at least one meltingpoint, Tm, in degrees Celsius, and a density, d, in grams/cubiccentimeter, wherein the numerical values of Tm and d correspond to therelationship:T _(m)≧−6880.9+14422(d)−7404.3(d)²
 25. The ethylene/α-olefin blockcopolymer of claim 1 characterized by having at least one fractionobtained by Temperature Rising Elution Fractionation (“TREF”), whereinthe fraction has a block index greater than about 0.3 and up to about1.0 and the ethylene/α-olefin block interpolymer has a molecular weightdistribution, M_(w)/M_(n), greater than about 1.4.
 26. Theethylene/α-olefin block interpolymer of claim 1, wherein the ethylenecontent is greater than about 50 mole percent.
 27. (canceled) 28.(canceled)
 29. The ethylene/α-olefin block interpolymer of claim 1,wherein the soft segments comprise less than 90% of ethylene by weight.30. (canceled)
 31. The ethylene/α-olefin block interpolymer of claim 1,wherein the hard segments and soft segments are randomly distributed.32. (canceled)
 33. (canceled)
 34. The ethylene/α-olefin blockinterpolymer of claim 1, wherein the block copolymer displays areflection spectrum that reaches a value of at least 12 percent withinthe region of infrared, visible or ultraviolet light.
 35. (canceled) 36.The ethylene/α-olefin block interpolymer of claim 1 wherein I₁₀/I₂>8.37. An article comprising the block interpolymer of claim
 1. 38. Thearticle of claim 37 wherein the article comprises a film, a moldedarticle, jewelry, a toy, an optical article, a decorative article or acombination thereof.
 39. The article of claim 38 wherein the opticalarticle comprises a photonic band gap material wherein the ratio of theindex of refraction of the segments having a difference in mole percentα-olefin content is 1.00 to 1.09 for a continuous set of wavelengthslying within a wavelength range of from about 100 nm to about 10 μm.